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Sample records for characterization vibrational spectroscopy

  1. Vibrational spectroscopy

    Science.gov (United States)

    Umesh P. Agarwal; Rajai Atalla

    2010-01-01

    Vibrational spectroscopy is an important tool in modern chemistry. In the past two decades, thanks to significant improvements in instrumentation and the development of new interpretive tools, it has become increasingly important for studies of lignin. This chapter presents the three important instrumental methods-Raman spectroscopy, infrared (IR) spectroscopy, and...

  2. Surface vibrational spectroscopy

    International Nuclear Information System (INIS)

    Erskine, J.L.

    1984-01-01

    A brief review of recent studies which combine measurements of surface vibrational energies with lattice dynamical calculations is presented. These results suggest that surface vibrational spectroscopy offers interesting prospects for use as a molecular-level probe of surface geometry, adsorbate bond distances and molecular orientations

  3. Characterization of polymer surface structure and surface mechanical behaviour by sum frequency generation surface vibrational spectroscopy and atomic force microscopy

    International Nuclear Information System (INIS)

    Opdahl, Aric; Koffas, Telly S; Amitay-Sadovsky, Ella; Kim, Joonyeong; Somorjai, Gabor A

    2004-01-01

    Sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM) have been used to study polymer surface structure and surface mechanical behaviour, specifically to study the relationships between the surface properties of polymers and their bulk compositions and the environment to which the polymer is exposed. The combination of SFG surface vibrational spectroscopy and AFM has been used to study surface segregation behaviour of polyolefin blends at the polymer/air and polymer/solid interfaces. SFG surface vibrational spectroscopy and AFM experiments have also been performed to characterize the properties of polymer/liquid and polymer/polymer interfaces, focusing on hydrogel materials. A method was developed to study the surface properties of hydrogel contact lens materials at various hydration conditions. Finally, the effect of mechanical stretching on the surface composition and surface mechanical behaviour of phase-separated polyurethanes, used in biomedical implant devices, has been studied by both SFG surface vibrational spectroscopy and AFM. (topical review)

  4. Recent Advances in the Characterization of Gaseous and Liquid Fuels by Vibrational Spectroscopy

    Directory of Open Access Journals (Sweden)

    Johannes Kiefer

    2015-04-01

    Full Text Available Most commercial gaseous and liquid fuels are mixtures of multiple chemical compounds. In recent years, these mixtures became even more complicated when the suppliers started to admix biofuels into the petrochemical basic fuels. As the properties of such mixtures can vary with composition, there is a need for reliable analytical technologies in order to ensure stable operation of devices such as internal combustion engines and gas turbines. Vibrational spectroscopic methods have proved their suitability for fuel characterization. Moreover, they have the potential to overcome existing limitations of established technologies, because they are fast and accurate, and they do not require sampling; hence they can be deployed as inline sensors. This article reviews the recent advances of vibrational spectroscopy in terms of infrared absorption (IR and Raman spectroscopy in the context of fuel characterization. The focus of the paper lies on gaseous and liquid fuels, which are dominant in the transportation sector and in the distributed generation of power. On top of an introduction to the physical principles and review of the literature, the techniques are critically discussed and compared with each other.

  5. Vibrational Spectroscopy of Ionic Liquids.

    Science.gov (United States)

    Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

    2017-05-24

    Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990's. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.

  6. 2008 Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Philip J. Reid

    2009-09-21

    The conference focuses on using vibrational spectroscopy to probe structure and dynamics of molecules in gases, liquids, and interfaces. The goal is to bring together a collection of researchers who share common interests and who will gain from discussing work at the forefront of several connected areas. The intent is to emphasize the insights and understanding that studies of vibrations provide about a variety of systems.

  7. Vibrational Spectroscopy and Astrobiology

    Science.gov (United States)

    Chaban, Galina M.; Kwak, D. (Technical Monitor)

    2001-01-01

    Role of vibrational spectroscopy in solving problems related to astrobiology will be discussed. Vibrational (infrared) spectroscopy is a very sensitive tool for identifying molecules. Theoretical approach used in this work is based on direct computation of anharmonic vibrational frequencies and intensities from electronic structure codes. One of the applications of this computational technique is possible identification of biological building blocks (amino acids, small peptides, DNA bases) in the interstellar medium (ISM). Identifying small biological molecules in the ISM is very important from the point of view of origin of life. Hybrid (quantum mechanics/molecular mechanics) theoretical techniques will be discussed that may allow to obtain accurate vibrational spectra of biomolecular building blocks and to create a database of spectroscopic signatures that can assist observations of these molecules in space. Another application of the direct computational spectroscopy technique is to help to design and analyze experimental observations of ice surfaces of one of the Jupiter's moons, Europa, that possibly contains hydrated salts. The presence of hydrated salts on the surface can be an indication of a subsurface ocean and the possible existence of life forms inhabiting such an ocean.

  8. Vibrational spectroscopy of proteins

    International Nuclear Information System (INIS)

    Schwaighofer, A.

    2013-01-01

    Two important steps for the development of a biosensor are the immobilization of the biological component (e.g. protein) on a surface and the enhancement of the signal to improve the sensitivity of detection. To address these subjects, the present work describes Fourier transform infrared (FTIR) investigations of several proteins bound to the surface of an attenuated total reflection (ATR) crystal. Furthermore, new nanostructured surfaces for signal enhancement were developed for use in FTIR microscopy. The mitochondrial redox-protein cytochrome c oxidase (CcO) was incorporated into a protein-tethered bilayer lipid membrane (ptBLM) on an ATR crystal featuring a roughened two-layer gold surface for signal enhancement. Electrochemical excitation by periodic potential pulses at different modulation frequencies was followed by time-resolved FTIR spectroscopy. Phase sensitive detection was used for deconvolution of the IR spectra into vibrational components. A model based on protonation-dependent chemical reaction kinetics could be fitted to the time evolution of IR bands attributed to several different redox centers of the CcO. Further investigations involved the odorant binding protein 14 (OBP14) of the honey bee (Apis mellifera), which was studied using ATR-FTIR spectroscopy and circular dichroism. OBP14 was found to be thermally stable up to 45 °C, thus permitting the potential application of this protein for the fabrication of biosensors. Thermal denaturation measurements showed that odorant binding increases the thermal stability of the OBP-odorant complex. In another project, plasmonic nanostructures were fabricated that enhance the absorbance in FTIR microscopy measurements. The nanostructures are composed of an array of round-shaped insulator and gold discs on top of a continuous gold layer. Enhancement factors of up to ⁓125 could be observed with self-assembled monolayers of dodecanethiol molecules immobilized on the gold surface (author) [de

  9. Bandshapes in vibrational spectroscopy

    International Nuclear Information System (INIS)

    Dijkman, F.G.

    1978-01-01

    A detailed account is given of the development of modern bandshape theories since 1965. An investigation into the relative contributions of statistical irreversible relaxation processes is described, for a series of molecules in which gradually the length of one molecular axis is increased. An investigation into the theoretical and experimental investigation of the broadening brought about by the effect of fluctuating intermolecular potentials on the vibrational frequency is also described. The effect of an intermolecular perturbative potential on anharmonic and Morse oscillators is discussed and the results are presented of a computation on the broadening of the vibrational band of some diatomic molecules in a rigid lattice type solvent. The broadening of the OH-stretching vibration in a number of aliphatic alcohols, the vibrational bandshapes of the acetylenic C-H stretching vibration and of the symmetric methyl stretching vibration are investigated. (Auth./ C.F.)

  10. Characterization of the calcification of cardiac valve bioprostheses by environmental scanning electron microscopy and vibrational spectroscopy.

    Science.gov (United States)

    Delogne, Christophe; Lawford, Patricia V; Habesch, Steven M; Carolan, Vikki A

    2007-10-01

    Bioprosthetic heart valve tissue and associated calcification were studied in their natural state, using environmental scanning electron microscopy (ESEM). Energy dispersive X-ray micro-analysis, X-ray diffraction, Fourier-transform infrared and Raman spectroscopy were used to characterize the various calcific deposits observed with ESEM. The major elements present in calcified valves were also analyzed by inductively coupled plasma-optical emission spectroscopy. To better understand the precursor formation of the calcific deposits, results from the elemental analyses were statistically correlated. ESEM revealed the presence of four broad types of calcium phosphate crystal morphology. In addition, two main patterns of organization of calcific deposits were observed associated with the collagen fibres. Energy dispersive X-ray micro-analysis identified the crystals observed by ESEM as salts containing mainly calcium and phosphate with ratios from 1.340 (possibly octacalcium phosphate, which has a Ca/P ratio of 1.336) to 2.045 (possibly hydroxyapatite with incorporation of carbonate and metal ion contaminants, such as silicon and magnesium, in the crystal lattice). Raman and fourier-transform infrared spectroscopy also identified the presence of carbonate and the analyses showed spectral features very similar to a crystalline hydroxyapatite spectrum, also refuting the presence of precursor phases such as beta-tricalcium phosphate, octacalcium phosphate and dicalcium phosphate dihydrate. The results of this study raised the possibility of the presence of precursor phases associated with the early stages of calcification.

  11. Surface vibrational spectroscopy (EELS)

    International Nuclear Information System (INIS)

    Okuyama, Hiroshi

    2006-01-01

    Adsorbed states of hydrogen on metal surfaces have been studied by means of electron energy loss spectroscopy (EELS). In this article, typical spectra and analysis as well as recent development are introduced. (author)

  12. Ultrafast infrared vibrational spectroscopy

    CERN Document Server

    Fayer, Michael D

    2013-01-01

    The past ten years or so have seen the introduction of multidimensional methods into infrared and optical spectroscopy. The technology of multidimensional spectroscopy is developing rapidly and its applications are spreading to biology and materials science. Edited by a recognized leader in the field and with contributions from top researchers, including experimentalists and theoreticians, this book presents the latest research methods and results and will serve as an excellent resource for other researchers.

  13. Characterizing Chemical Similarity with Vibrational Spectroscopy: New Insights into the Substituent Effects in Monosubstituted Benzenes.

    Science.gov (United States)

    Tao, Yunwen; Zou, Wenli; Cremer, Dieter; Kraka, Elfi

    2017-10-26

    A novel approach is presented to assess chemical similarity based the local vibrational mode analysis developed by Konkoli and Cremer. The local mode frequency shifts are introduced as similarity descriptors that are sensitive to any electronic structure change. In this work, 59 different monosubstituted benzenes are compared. For a subset of 43 compounds, for which experimental data was available, the ortho-/para- and meta-directing effect in electrophilic aromatic substitution reactions could be correctly reproduced, proving the robustness of the new similarity index. For the remaining 16 compounds, the directing effect was predicted. The new approach is broadly applicable to all compounds for which either experimental or calculated vibrational frequency information is available.

  14. Time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tokmakoff, Andrei [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Champion, Paul [Northeastern Univ., Boston, MA (United States); Heilweil, Edwin J. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Nelson, Keith A. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ziegler, Larry [Boston Univ., MA (United States)

    2009-05-14

    This document contains the Proceedings from the 14th International Conference on Time-Resolved Vibrational Spectroscopy, which was held in Meredith, NH from May 9-14, 2009. The study of molecular dynamics in chemical reaction and biological processes using time-resolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE's Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation of reactive intermediates in radiation chemistry. In addition, time-resolved spectroscopy is central to all fiveof DOE's grand challenges for fundamental energy science. The Time-Resolved Vibrational Spectroscopy conference is organized biennially to bring the leaders in this field from around the globe together with young scientists to discuss the most recent scientific and technological advances. The latest technology in ultrafast infrared, Raman, and terahertz spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.

  15. Vibrational Characterizations of Zn0.72Li0.28O/Si Thin Films Studied by Fourier Transform Raman Spectroscopy

    International Nuclear Information System (INIS)

    Myo Myat Thet; Win Kyaw; Yin Maung Maung; Ko Ko Kyaw Soe

    2008-03-01

    The Zn0.72Li0.28O/Si (x = 0.28mol%) thin layers were fabricated on p-Si(100) substrate with five different process temperature. Vibrational characterizations of those thin films were investigated by FT- Raman spectroscopy. The resulted spectral line characters have been compared with that of Zn0.72Li0.28O/Glass thin films. Some vibrational motions of starting materials and final(candidate) thin films molecules were found in two substrates of glass and Si and vibrational frequencies were assigned by using molecular spectroscopy. Most of the frequencies of starting and final materials were found to be shifted in each of the films of two different substrates.

  16. Characterizing interstate vibrational coherent dynamics of surface adsorbed catalysts by fourth-order 3D SFG spectroscopy

    Science.gov (United States)

    Li, Yingmin; Wang, Jiaxi; Clark, Melissa L.; Kubiak, Clifford P.; Xiong, Wei

    2016-04-01

    We report the first fourth-order 3D SFG spectroscopy of a monolayer of the catalyst Re(diCN-bpy)(CO)3Cl on a gold surface. Besides measuring the vibrational coherences of single vibrational modes, the fourth-order 3D SFG spectrum also measures the dynamics of interstate coherences and vibrational coherences states between two vibrational modes. By comparing the 3D SFG to the corresponding 2D and third-order 3D IR spectroscopy of the same molecules in solution, we found that the interstate coherences exist in both liquid and surface systems, suggesting that the interstate coherence is not disrupted by surface interactions. However, by analyzing the 3D spectral lineshape, we found that the interstate coherences also experience non-negligible homogenous dephasing dynamics that originate from surface interactions. This unique ability of determining interstate vibrational coherence dynamics of the molecular monolayer can help in understanding of how energy flows within surface catalysts and other molecular monolayers.

  17. Identification and Partial Structural Characterization of Mass Isolated Valsartan and Its Metabolite with Messenger Tagging Vibrational Spectroscopy

    Science.gov (United States)

    Gorlova, Olga; Colvin, Sean M.; Brathwaite, Antonio; Menges, Fabian S.; Craig, Stephanie M.; Miller, Scott J.; Johnson, Mark A.

    2017-08-01

    Recent advances in the coupling of vibrational spectroscopy with mass spectrometry create new opportunities for the structural characterization of metabolites with great sensitivity. Previous studies have demonstrated this scheme on 300 K ions using very high power free electron lasers in the fingerprint region of the infrared. Here we extend the scope of this approach to a single investigator scale as well as extend the spectral range to include the OH stretching fundamentals. This is accomplished by detecting the IR absorptions in a linear action regime by photodissociation of weakly bound N2 molecules, which are attached to the target ions in a cryogenically cooled, rf ion trap. We consider the specific case of the widely used drug Valsartan and two isomeric forms of its metabolite. Advantages and challenges of the cold ion approach are discussed, including disentangling the role of conformers and the strategic choices involved in the selection of the charging mechanism that optimize spectral differentiation among candidate structural isomers. In this case, the Na+ complexes are observed to yield sharp resonances in the high frequency NH and OH stretching regions, which can be used to easily differentiate between two isomers of the metabolite. [Figure not available: see fulltext.

  18. Nanoscale chemical and mechanical characterization of thin films:sum frequency generation (SFG) vibrational spectroscopy at buriedinterfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kweskin, Sasha Joseph [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Sum frequency generation (SFG) surface vibrational spectroscopy was used to characterize interfaces pertinent to current surface engineering applications, such as thin film polymers and novel catalysts. An array of advanced surface science techniques like scanning probe microscopy (SPM), x-ray photoelectron spectroscopy (XPS), gas chromatography (GC) and electron microscopy were used to obtain experimental measurements complementary to SFG data elucidating polymer and catalyst surface composition, surface structure, and surface mechanical behavior. Experiments reported in this dissertation concentrate on three fundamental questions: (1) How does the interfacial molecular structure differ from that of the bulk in real world applications? (2) How do differences in chemical environment affect interface composition or conformation? (3) How do these changes correlate to properties such as mechanical or catalytic performance? The density, surface energy and bonding at a solid interface dramatically alter the polymer configuration, physics and mechanical properties such as surface glass transition, adhesion and hardness. The enhanced sensitivity of SFG at the buried interface is applied to three systems: a series of acrylates under compression, the compositions and segregation behavior of binary polymer polyolefin blends, and the changes in surface structure of a hydrogel as a function of hydration. In addition, a catalytically active thin film of polymer coated nanoparticles is investigated to evaluate the efficacy of SFG to provide in situ information for catalytic reactions involving small mass adsorption and/or product development. Through the use of SFG, in situ total internal reflection (TIR) was used to increase the sensitivity of SFG and provide the necessary specificity to investigate interfaces of thin polymer films and nanostructures previously considered unfeasible. The dynamic nature of thin film surfaces is examined and it is found that the non

  19. Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials

    Science.gov (United States)

    Sronsri, Chuchai; Boonchom, Banjong

    2018-04-01

    A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn0.9Mg0.1HPO4·3H2O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn1.8Mg0.2P2O7 and LiMn0.9Mg0.1PO4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO42-, H2O, P2O74- and PO43- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn0.9Mg0.1HPO4·3H2O was observed in the orthorhombic crystal system with the space group of Pbca (D2h15). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO42- was observed as Cs. For the HPO42- unit, the correlation filed splitting analysis of type C3v - Cs - D2h15 was calculated and had 96 internal modes, whereas H2O in the above hydrate was symbolized as C2v - Cs - D2h15 and had 24 modes. The symbol C2v - Cs - C2h3 was used for the correlation filed splitting analysis of P2O74- in Mn1.8Mg0.2P2O7 (monoclinic, C2/m (C2h3), Z = 2, and 42 modes). Finally, the symbol Td - Cs - D2h16 was used for the correlation filed splitting analysis of PO43- in LiMn0.9Mg0.1PO4 (orthorhombic, Pnma (D2h16), Z = 4, and 36 modes).

  20. Vibrational spectroscopy as a probe to rapidly detect, identify, and characterize micro-organisms

    Science.gov (United States)

    Sockalingum, Ganesh D.; Lamfarraj, Hasnae; Beljebbar, Abdelilah; Pina, Patrick; Delavenne, Marc; Witthuhn, Fabienne; Allouch, Pierre; Manfait, Michel

    1999-04-01

    Fast and exact identification of a great number of microorganisms is becoming a serious challenge. Differentiation and identification of microorganisms is today mainly achieved by the use of a variety of distinct techniques based on morphological, serological aspects and a set of biochemical test. Vibrational spectroscopic techniques can be complementary and useful methods in this field due to their rapidity, 'fingerprinting' capabilities, and the molecular information that they can provide. Using SERS at Ag colloids, we have conducted pilot studies to rapidly detect and identify bacterial clinical strains. Using a Raman microspectrometer equipped with a He/Ne laser, a first attempt to record SERS spectra was made on colloidal solutions. Spectra were of good quality but not very reproducible due to the movement of the microorganisms. Strains were then put in presence of Ag colloids and direct on-plate analysis was performed. Spectra were more reproducible, with diminished fluorescence, and reveal characteristic cellular-level information. Different growth conditions and colloid preparations have been tested. Pseudomonas aeruginosa and Escherichia coli clinical strains, responsible for nosocomial infections, have been our first test samples. An attempt has also been made to record SERS data from gold colloids in view of future measurement in the near-IR. Spectroscopic data are compared with ATR-FTIR results.

  1. Vibrational Micro-Spectroscopy of Human Tissues Analysis: Review.

    Science.gov (United States)

    Bunaciu, Andrei A; Hoang, Vu Dang; Aboul-Enein, Hassan Y

    2017-05-04

    Vibrational spectroscopy (Infrared (IR) and Raman) and, in particular, micro-spectroscopy and micro-spectroscopic imaging have been used to characterize developmental changes in tissues, to monitor these changes in cell cultures and to detect disease and drug-induced modifications. The conventional methods for biochemical and histophatological tissue characterization necessitate complex and "time-consuming" sample manipulations and the results are rarely quantifiable. The spectroscopy of molecular vibrations using mid-IR or Raman techniques has been applied to samples of human tissue. This article reviews the application of these vibrational spectroscopic techniques for analysis of biological tissue published between 2005 and 2015.

  2. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    Science.gov (United States)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

  3. Vibrational Spectroscopy of Chromatographic Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jeanne E. Pemberton

    2011-03-10

    Chromatographic separations play a central role in DOE-supported fundamental research related to energy, biological systems, the environment, and nuclear science. The overall portfolio of research activities in the Separations and Analysis Program within the DOE Office of Basic Energy Sciences includes support for activities designed to develop a molecular-level understanding of the chemical processes that underlie separations for both large-scale and analytical-scale purposes. The research effort funded by this grant award was a continuation of DOE-supported research to develop vibrational spectroscopic methods to characterize the interfacial details of separations processes at a molecular level.

  4. Sum frequency generation for surface vibrational spectroscopy

    International Nuclear Information System (INIS)

    Hunt, J.H.; Guyot-Sionnest, P.; Shen, Y.R.

    1987-01-01

    Surface vibrational spectroscopy is one of the best means for characterizing molecular adsorbates. For this reason, many techniques have been developed in the past. However, most of them suffer from poor sensitivity, low spectral and temporal resolution, and applications limited to vacuum solid interfaces. Recently, the second harmonic generation (SHG) technique was proved repeatedly to be a simple but versatile surface probe. It is highly sensitive and surface specific; it is also capable of achieving high temporal, spatial, and spectral resolution. Being an optical technique, it can be applied to any interface accessible by light. The only serious drawback is its lack of molecular selectivity. An obvious remedy is the extension of the technique to IR-visible sum frequency generation (SFG). Surface vibrational spectroscopy with submonolayer sensitivity is then possible using SFG with the help of a tunable IR laser. The authors report here an SFG measurement of the C-H stretch vibration of monolayers of molecules at air-solid and air-liquid interfaces

  5. General principles of vibrational spectroscopies

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Schoonheydt, R.A.

    2000-01-01

    Atoms in molecules and solids do not remain in fixed relative positions, but vibrate about some mean position. This vibrational motion is quantized and at room temperature, most of the molecules in a given sample are in their lowest vibrational state. Absorption of electromagnetic radiation with

  6. Vibrational spectroscopy in the electron microscope.

    Science.gov (United States)

    Krivanek, Ondrej L; Lovejoy, Tracy C; Dellby, Niklas; Aoki, Toshihiro; Carpenter, R W; Rez, Peter; Soignard, Emmanuel; Zhu, Jiangtao; Batson, Philip E; Lagos, Maureen J; Egerton, Ray F; Crozier, Peter A

    2014-10-09

    Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample--that is, for 'aloof' spectroscopy that largely avoids radiation damage.

  7. Spectroscopy and reactions of vibrationally excited transient molecules

    Energy Technology Data Exchange (ETDEWEB)

    Dai, H.L. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    Spectroscopy, energy transfer and reactions of vibrationally excited transient molecules are studied through a combination of laser-based excitation techniques and efficient detection of emission from the energized molecules with frequency and time resolution. Specifically, a Time-resolved Fourier Transform Emission Spectroscopy technique has been developed for detecting dispersed laser-induced fluorescence in the IR, visible and UV regions. The structure and spectroscopy of the excited vibrational levels in the electronic ground state, as well as energy relaxation and reactions induced by specific vibronic excitations of a transient molecule can be characterized from time-resolved dispersed fluorescence in the visible and UV region. IR emissions from highly vibrational excited levels, on the other hand, reveal the pathways and rates of collision induced vibrational energy transfer.

  8. Structural characterization, vibrational spectroscopy accomplished with DFT calculation, thermal and dielectric behaviors in a new organic-inorganic tertrapropylammonium aquapentachlorostannate dihydrate compound

    Energy Technology Data Exchange (ETDEWEB)

    Hajlaoui, Sondes, E-mail: hajlaouisondes@yahoo.fr [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia); Chaabane, Iskandar [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia); Lhoste, Jérôme; Bulou, Alain [LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085, Le Mans, Cedex 9 (France); Guidara, Kamel [Unité de recherche de la matière condensée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000, Sfax (Tunisia)

    2016-09-15

    In this work a novel compound tertrapropylammonium aquapentachlorostannate dihydrate was synthesized and characterized by; single crystal X-ray diffraction, vibrational spectroscopy, differential scanning calorimetric and dielectric measurement. The crystal structure refinement at room temperature reveled that this later belongs to the monoclinic compound with P121/c1 space group with the following unit cell parameters a = 8.2699(3) Å, b = 12.4665(4) Å, c = 22.3341(7) Å and β = 92.94(0)°. The crystal arrangement can be described by stacked organic-inorganic layers in the c direction with two independent water molecules placed between each two layers. The detailed interpretations of the vibrational properties of the studied compound were performed using density functional theory (DFT) with the B3LYP/LanL2DZ basis set, and has enabled us to make the detailed assignments by comparative study of the experimental and calculated Raman and IR spectra. The differential scanning calorimetry (DSC) measurement disclosed two anomalies in the temperature range 356–376 (T{sub 1}) K and at 393 K (T{sub 2}) characterized by the dehydration of the sample and probably a reconstruction of a new structure after T{sub 2} transition. The temperature dependences of dielectric permittivity show a relaxation process around T{sub 2} anomaly indicating the occurrence of the disorder at high temperature. The dependence of the exponent m(T) on temperature, extracted from the straight lines of log(ε″) with log (ω), suggests that the correlated barrier hopping is the appropriate model for the conduction mechanism. - Highlights: • The single-crystal X-ray diffraction has been performed. • The assignments of the vibration modes based on DFT were reported and discussed. • Differential scanning calorimetric reveals the presence of two endothermic peaks. • The electric permittivity was studied using the impedance measurements. • The CBH is the appropriate model for the conduction

  9. Two-dimensional vibrational-electronic spectroscopy

    Science.gov (United States)

    Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.; Khalil, Munira

    2015-10-01

    Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([FeIII(CN)6]3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5FeIICNRuIII(NH3)5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

  10. Two-dimensional vibrational-electronic spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.; Khalil, Munira, E-mail: mkhalil@uw.edu [Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195 (United States)

    2015-10-21

    Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (ν{sub CN}) and either a ligand-to-metal charge transfer transition ([Fe{sup III}(CN){sub 6}]{sup 3−} dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN){sub 5}Fe{sup II}CNRu{sup III}(NH{sub 3}){sub 5}]{sup −} dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific ν{sub CN} modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a

  11. Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Hui; Lewis, Nicholas H. C.; Oliver, Thomas A. A.; Fleming, Graham R., E-mail: grfleming@lbl.gov [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, Californial 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2015-05-07

    Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate the slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.

  12. Theory for Nonlinear Spectroscopy of Vibrational Polaritons

    OpenAIRE

    Ribeiro, RF; Dunkelberger, AD; Xiang, B; Xiong, W; Simpkins, BS; Owrutsky, JC; Yuen-Zhou, J

    2017-01-01

    Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. In this letter, we develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum La...

  13. Vibrations of bioionic liquids by ab initio molecular dynamics and vibrational spectroscopy.

    Science.gov (United States)

    Tanzi, Luana; Benassi, Paola; Nardone, Michele; Ramondo, Fabio

    2014-12-26

    Density functional theory and vibrational spectroscopy are used to investigate a class of bioionic liquids consisting of a choline cation and carboxylate anions. Through quantum mechanical studies of motionless ion pairs and molecular dynamics of small portions of the liquid, we have characterized important structural features of the ionic liquid. Hydrogen bonding produces stable ion pairs in the liquid and induces vibrational features of the carboxylate groups comparable with experimental results. Infrared and Raman spectra of liquids have been measured, and main bands have been assigned on the basis of theoretical spectra.

  14. Toward yrast spectroscopy in soft vibrational nuclei

    International Nuclear Information System (INIS)

    Marumori, Toshio; Kuriyama, Atsushi; Sakata, Fumihiko.

    1979-10-01

    In a formally parallel way with that exciting progress has been recently achieved in understanding the yrast spectra of the rotational nuclei in terms of the quasi-particle motion in the rotating frame, an attempt to understand the yrast spectra of the vibrational nuclei in terms of the quasi-particle motion is proposed. The essential idea is to introduce the quasi-particle motion in a generalized vibrating frame, which can be regarded as a rotating frame in the gauge space of ''physical'' phonons where the number of the physical phonons plays the role of the angular momentum. On the basis of a simple fundamental principle called as the ''invariance principle of the Schroedinger equation'', which leads us to the ''maximal decoupling'' between the physical phonon and the intrinsic modes, it is shown that the vibrational frame as well as the physical-phonon-number operator represented by the quasi-particles can be self-consistently determined. A new scope toward the yrast spectroscopy of the vibrational nuclei in terms of the quasi-particle motion is discussed. (author)

  15. Spectroscopie de vibration infrarouge du silicium amorphe ...

    African Journals Online (AJOL)

    ... évaporé (a-Si:H) préparées dans un bâti ultra-vide (UHV). L'hydrogène atomique est obtenu à l'aide d'un plasma dans un tube à décharge dirigé vers le porte-substrat. Les fréquences de vibrations et la nature des liaisons Si-H ont été analysées à partir des mesures de spectroscopie infrarouge à transformée de Fourier.

  16. Vibrational spectroscopy in diagnosis and screening

    CERN Document Server

    Severcan, F

    2012-01-01

    In recent years there has been a tremendous growth in the use of vibrational spectroscopic methods for diagnosis and screening. These applications range from diagnosis of disease states in humans, such as cancer, to rapid identification and screening of microorganisms. The growth in such types of studies has been possible thanks to advances in instrumentation and associated computational and mathematical tools for data processing and analysis. This volume of Advances in Biomedical Spectroscopy contains chapters from leading experts who discuss the latest advances in the application of Fourier

  17. Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-Dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling

    KAUST Repository

    Mohammed, Omar F.

    2014-05-01

    We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide a general description of the electronic excited-state dynamics based on a systematic analysis of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S 2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S 1 state where DHAQ exhibits ESIHT dynamics. In this equilibration process, the excited-state population is distributed between the 9,10-quinone (S2) and 1,10-quinone (S1) states while undergoing vibrational energy redistribution, vibrational cooling, and solvation dynamics on the 0.1-50 ps time scale. Transient UV/vis pump-probe data in methanol also suggest additional relaxation dynamics on the subnanosecond time scale, which we tentatively ascribe to hydrogen bond dynamics of DHAQ with the protic solvent, affecting the equilibrium population dynamics within the S2 and S1 electronic excited states. Ultimately, the two excited singlet states decay with a solvent-dependent time constant ranging from 139 to 210 ps. The concomitant electronic ground-state recovery is, however, only partial because a large fraction of the population relaxes to the first triplet state. From the similarity of the time scales involved, we conjecture that the solvent plays a crucial role in breaking the intramolecular hydrogen bond of DHAQ during the S2/S1 relaxation to either the ground or triplet state. © 2014 American Chemical Society.

  18. Vibrational spectroscopy: a clinical tool for cancer diagnostics.

    Science.gov (United States)

    Kendall, Catherine; Isabelle, Martin; Bazant-Hegemark, Florian; Hutchings, Joanne; Orr, Linda; Babrah, Jaspreet; Baker, Rebecca; Stone, Nicholas

    2009-06-01

    Vibrational spectroscopy techniques have demonstrated potential to provide non-destructive, rapid, clinically relevant diagnostic information. Early detection is the most important factor in the prevention of cancer. Raman and infrared spectroscopy enable the biochemical signatures from biological tissues to be extracted and analysed. In conjunction with advanced chemometrics such measurements can contribute to the diagnostic assessment of biological material. This paper also illustrates the complementary advantage of using Raman and FTIR spectroscopy technologies together. Clinical requirements are increasingly met by technological developments which show promise to become a clinical reality. This review summarises recent advances in vibrational spectroscopy and their impact on the diagnosis of cancer.

  19. Seventh international conference on time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, R.B.; Martinez, M.A.D.; Shreve, A.; Woodruff, W.H. [comps.

    1997-04-01

    The International Conference on Time-Resolved Vibrational Spectroscopy (TRVS) is widely recognized as the major international forum for the discussion of advances in this rapidly growing field. The 1995 conference was the seventh in a series that began at Lake Placid, New York, 1982. Santa Fe, New Mexico, was the site of the Seventh International Conference on Time-Resolved Vibrational Spectroscopy, held from June 11 to 16, 1995. TRVS-7 was attended by 157 participants from 16 countries and 85 institutions, and research ranging across the full breadth of the field of time-resolved vibrational spectroscopy was presented. Advances in both experimental capabilities for time-resolved vibrational measurements and in theoretical descriptions of time-resolved vibrational methods continue to occur, and several sessions of the conference were devoted to discussion of these advances and the associated new directions in TRVS. Continuing the interdisciplinary tradition of the TRVS meetings, applications of time-resolved vibrational methods to problems in physics, biology, materials science, and chemistry comprised a large portion of the papers presented at the conference.

  20. Two-dimensional infrared spectroscopy of vibrational polaritons.

    Science.gov (United States)

    Xiang, Bo; Ribeiro, Raphael F; Dunkelberger, Adam D; Wang, Jiaxi; Li, Yingmin; Simpkins, Blake S; Owrutsky, Jeffrey C; Yuen-Zhou, Joel; Xiong, Wei

    2018-04-19

    We report experimental 2D infrared (2D IR) spectra of coherent light-matter excitations--molecular vibrational polaritons. The application of advanced 2D IR spectroscopy to vibrational polaritons challenges and advances our understanding in both fields. First, the 2D IR spectra of polaritons differ drastically from free uncoupled excitations and a new interpretation is needed. Second, 2D IR uniquely resolves excitation of hybrid light-matter polaritons and unexpected dark states in a state-selective manner, revealing otherwise hidden interactions between them. Moreover, 2D IR signals highlight the impact of molecular anharmonicities which are applicable to virtually all molecular systems. A quantum-mechanical model is developed which incorporates both nuclear and electrical anharmonicities and provides the basis for interpreting this class of 2D IR spectra. This work lays the foundation for investigating phenomena of nonlinear photonics and chemistry of molecular vibrational polaritons which cannot be probed with traditional linear spectroscopy.

  1. Vibrational spectroscopy on intermolecular interactions in solutions and at interfaces

    NARCIS (Netherlands)

    Nissink, Johannes Wilhelmus Maria

    1999-01-01

    In recent years, considerable progress has been made in the areas of molecular recognition and surface analysis. These fields meet in the field of sensor development, where the interaction between molecules and a suitably modified surface is of utmost importance. Vibrational spectroscopy is quite

  2. Crystal structure, thermal behaviour, vibrational spectroscopy and ...

    Indian Academy of Sciences (India)

    2018-05-23

    May 23, 2018 ... modes corresponding to the kröhnkite is identified by the IR and Raman spectroscopies in the frequency ranges ..... The two weak bands near 1227 and 1202 cm ... ciated with the hydroxyl groups are taken into consideration.

  3. Characterization of the molecular structure and mechanical properties of polymer surfaces and protein/polymer interfaces by sum frequency generation vibrational spectroscopy and atomic force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Koffas, Telly Stelianos [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and other complementary surface-sensitive techniques have been used to study the surface molecular structure and surface mechanical behavior of biologically-relevant polymer systems. SFG and AFM have emerged as powerful analytical tools to deduce structure/property relationships, in situ, for polymers at air, liquid and solid interfaces. The experiments described in this dissertation have been performed to understand how polymer surface properties are linked to polymer bulk composition, substrate hydrophobicity, changes in the ambient environment (e.g., humidity and temperature), or the adsorption of macromolecules. The correlation of spectroscopic and mechanical data by SFG and AFM can become a powerful methodology to study and engineer materials with tailored surface properties. The overarching theme of this research is the interrogation of systems of increasing structural complexity, which allows us to extend conclusions made on simpler model systems. We begin by systematically describing the surface molecular composition and mechanical properties of polymers, copolymers, and blends having simple linear architectures. Subsequent chapters focus on networked hydrogel materials used as soft contact lenses and the adsorption of protein and surfactant at the polymer/liquid interface. The power of SFG is immediately demonstrated in experiments which identify the chemical parameters that influence the molecular composition and ordering of a polymer chain's side groups at the polymer/air and polymer/liquid interfaces. In general, side groups with increasingly greater hydrophobic character will be more surface active in air. Larger side groups impose steric restrictions, thus they will tend to be more randomly ordered than smaller hydrophobic groups. If exposed to a hydrophilic environment, such as water, the polymer chain will attempt to orient more of its hydrophilic groups to

  4. Vibrational spectroscopy at high external pressures the diamond anvil cell

    CERN Document Server

    Ferraro, John R

    1984-01-01

    Vibrational Spectroscopy at High External Pressures: The Diamond Anvil Cell presents the effects of high pressure on the vibrational properties of materials as accomplished in a diamond anvil cell (DAC). The DAC serves the dual purpose of generating the pressures and being transparent to infrared radiation, allowing the observation of changes caused by pressure. The optical probes highlighted will deal principally with infrared and Raman scattering, although some observations in the visible region will also be presented. The book begins with a discussion of the effects of pressure and pres

  5. Molecular structure and vibrational spectroscopy of isoproturon

    Science.gov (United States)

    Vrielynck, L.; Dupuy, N.; Kister, J.; Nowogrocki, G.

    2006-05-01

    The crystal structure of isoproturon [ N-(4-isopropylphenyl)- N', N'-dimethylurea] has been determined: the compound crystallizes in the space group Pbca with unit cell parameters a=10.186(2) Å, b=11.030(2) Å, c=20.981(4) Å. The structure was solved and refined down to R1=0.0508 and ωR2=0.12470 for 3056 reflections. The crystalline molecular network of this pesticide is stabilized, as for many molecules of the same family, by π-π interactions but especially by a medium-strong N-H⋯C dbnd6 O intermolecular hydrogen bond (2.14 Å). The X-ray parameters were then compared with the results of DFT quantum chemical calculation computed with the GAUSSIAN 94 package. A tentative assignment of the ATR-FT-IR and Raman spectra was proposed supported by vibrational mode calculation and spectroscopic data on benzenic and urea derivatives available in the literature. The presence of a tight band around 3300 cm -1, which can be assigned to the NH bond stretching mode as well as the low frequency position of the amide I band at 1640 cm -1, sensitive to solvent polarity, confirms the existence of a quite strong intermolecular hydrogen bond between neighboring molecules in the crystal of isoproturon.

  6. Development, implementation, and characterization of a standalone embedded viscosity measurement system based on the impedance spectroscopy of a vibrating wire sensor

    Science.gov (United States)

    Santos, José; Janeiro, Fernando M.; Ramos, Pedro M.

    2015-10-01

    This paper presents an embedded liquid viscosity measurement system based on a vibrating wire sensor. Although multiple viscometers based on different working principles are commercially available, there is still a market demand for a dedicated measurement system capable of performing accurate, fast measurements and requiring little or no operator training for simple systems and solution monitoring. The developed embedded system is based on a vibrating wire sensor that works by measuring the impedance response of the sensor, which depends on the viscosity and density of the liquid in which the sensor is immersed. The core of the embedded system is a digital signal processor (DSP) which controls the waveform generation and acquisitions for the measurement of the impedance frequency response. The DSP also processes the acquired waveforms and estimates the liquid viscosity. The user can interact with the measurement system through a keypad and an LCD or through a computer with a USB connection for data logging and processing. The presented system is tested on a set of viscosity standards and the estimated values are compared with the standard manufacturer specified viscosity values. A stability study of the measurement system is also performed.

  7. Development, implementation, and characterization of a standalone embedded viscosity measurement system based on the impedance spectroscopy of a vibrating wire sensor

    International Nuclear Information System (INIS)

    Santos, José; Ramos, Pedro M; Janeiro, Fernando M

    2015-01-01

    This paper presents an embedded liquid viscosity measurement system based on a vibrating wire sensor. Although multiple viscometers based on different working principles are commercially available, there is still a market demand for a dedicated measurement system capable of performing accurate, fast measurements and requiring little or no operator training for simple systems and solution monitoring. The developed embedded system is based on a vibrating wire sensor that works by measuring the impedance response of the sensor, which depends on the viscosity and density of the liquid in which the sensor is immersed. The core of the embedded system is a digital signal processor (DSP) which controls the waveform generation and acquisitions for the measurement of the impedance frequency response. The DSP also processes the acquired waveforms and estimates the liquid viscosity. The user can interact with the measurement system through a keypad and an LCD or through a computer with a USB connection for data logging and processing. The presented system is tested on a set of viscosity standards and the estimated values are compared with the standard manufacturer specified viscosity values. A stability study of the measurement system is also performed. (paper)

  8. Resonance tunneling electron-vibrational spectroscopy of polyoxometalates.

    Science.gov (United States)

    Dalidchik, F I; Kovalevskii, S A; Balashov, E M

    2017-05-21

    The tunneling spectra of the ordered monolayer films of decamolybdodicobaltate (DMDC) compounds deposited from aqueous solutions on HOPG were measured by scanning tunnel microscopy in air. The DMDC spectra, as well as the tunneling spectra of other polyoxometalates (POMs), exhibit well-defined negative differential resistances (NDRs). The mechanism of formation of these spectral features was established from the collection of revealed NDR dependences on the external varying parameters and found to be common to all systems exhibiting Wannier-Stark localization. A model of biresonance tunneling was developed to provide an explanation for the totality of experimental data, both the literature and original, on the tunneling POM probing. A variant of the tunneling electron-vibrational POM spectroscopy was proposed allowing the determination of the three basic energy parameters-energy gaps between the occupied and unoccupied states, frequencies of the vibrational transitions accompanying biresonance electron-tunneling processes, and electron-vibrational interaction constants on the monomolecular level.

  9. On selection rules in vibrational and rotational molecular spectroscopy

    International Nuclear Information System (INIS)

    Guichardet, A.

    1986-01-01

    The aim of this work is a rigorous proof of the Selection Rules in Molecular Spectroscopy (Vibration and Rotation). To get this we give mathematically rigorous definitions of the (tensor) transition operators, in this case the electric dipole moment; this is done, firstly by considering the molecule as a set of point atomic kernels performing arbitrary motions, secondly by limiting ourselves either to infinitesimal vibration motions, or to arbitrary rotation motions. Then the selection rules follow from an abstract formulation of the Wigner-Eckart theorem. In a last paragraph we discuss the problem of separating vibration and rotation motions; very simple ideas from Differential Geometry, linked with the ''slice theorem'', allow us to define the relative speeds, the solid motions speeds, the Coriolis energies and the moving Eckart frames [fr

  10. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Science.gov (United States)

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  11. Electronic and vibrational spectroscopy and vibrationally mediated photodissociation of V+(OCO).

    Science.gov (United States)

    Citir, Murat; Altinay, Gokhan; Metz, Ricardo B

    2006-04-20

    Electronic spectra of gas-phase V+(OCO) are measured in the near-infrared from 6050 to 7420 cm(-1) and in the visible from 15,500 to 16,560 cm(-1), using photofragment spectroscopy. The near-IR band is complex, with a 107 cm(-1) progression in the metal-ligand stretch. The visible band shows clearly resolved vibrational progressions in the metal-ligand stretch and rock, and in the OCO bend, as observed by Brucat and co-workers. A vibrational hot band gives the metal-ligand stretch frequency in the ground electronic state nu3'' = 210 cm(-1). The OCO antisymmetric stretch frequency in the ground electronic state (nu1'') is measured by using vibrationally mediated photodissociation. An IR laser vibrationally excites ions to nu1'' = 1. Vibrationally excited ions selectively dissociate following absorption of a second, visible photon at the nu1' = 1 CO2, due to interaction with the metal. Larger blue shifts observed for complexes with fewer ligands agree with trends seen for larger V+(OCO)n clusters.

  12. Structural characterization of rondorfite, calcium silica chlorine mineral containing magnesium in tetrahedral position [MgO4]6-, with the aid of the vibrational spectroscopies and fluorescence.

    Science.gov (United States)

    Dulski, M; Bulou, A; Marzec, K M; Galuskin, E V; Wrzalik, R

    2013-01-15

    Raman and infrared spectra of rondorfite Ca8Mg(SiO4)4Cl2, a calcium chlorosilica mineral containing magnesium in tetrahedral position, has been studied in terms of spectra-structure relations. Raman spectra have been measured at different excited laser lines: 780 nm, 532 nm, 488 nm and 457 nm. This mineral is characterized by a single sharp intense Raman band at 863 cm(-1) assigned to the ν1 [SiO4]4- (Ag) symmetric stretching mode in the magnesiosilicate pentamer. Due to symmetry restriction the other Raman bands have a small intensity. Two Raman bands observed at 564 cm(-1) and 526 cm(-1) are associated simultaneously with ν4 [MgO4]6- and ν4 [SiO4]4- symmetric and antisymmetric modes where magnesium occurs in the tetrahedral configuration. The weak bands at 422 cm(-1) and 386 cm(-1) are associated with the ν2 bending mode of CaO6 in octahedral configuration, respectively. Moreover the infrared spectrum shows very weak bands associated with the hydroxyl group and/or water molecule. Additionally, the strong fluorescence phenomenon was observed and related to the presence of chlorine atoms, magnesium Mg2+ ions in atypical configuration or point defects. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Vibrational spectroscopy and structural analysis of complex uranium compounds (review)

    International Nuclear Information System (INIS)

    Umreiko, D.S.; Nikanovich, M.V.

    1985-01-01

    The paper reports on the combined application of experimental and theoretical methods of vibrational spectroscopy together with low-temperature luminescence data to determine the characteristic features of the formation and structure of complex systems, not only containing ligands directly coordinated to the CA uranium, but also associated with the extraspherical polyatomic electrically charged particles: organic cations. These include uranyl complexes and heterocyclical amines. Studied here were compounds of tetra-halouranylates with pyridine and its derivates, as well as dipyridyl, quinoline and phenanthroline. Structural schemes are also proposed for other uranyl complexes with protonated heterocyclical amines with a more complicated composition, which correctly reflect their spectroscopic properties

  14. [Structure analysis of disease-related proteins using vibrational spectroscopy].

    Science.gov (United States)

    Hiramatsu, Hirotsugu

    2014-01-01

    Analyses of the structure and properties of identified pathogenic proteins are important for elucidating the molecular basis of diseases and in drug discovery research. Vibrational spectroscopy has advantages over other techniques in terms of sensitivity of detection of structural changes. Spectral analysis, however, is complicated because the spectrum involves a substantial amount of information. This article includes examples of structural analysis of disease-related proteins using vibrational spectroscopy in combination with additional techniques that facilitate data acquisition and analysis. Residue-specific conformation analysis of an amyloid fibril was conducted using IR absorption spectroscopy in combination with (13)C-isotope labeling, linear dichroism measurement, and analysis of amide I band features. We reveal a pH-dependent property of the interacting segment of an amyloidogenic protein, β2-microglobulin, which causes dialysis-related amyloidosis. We also reveal the molecular mechanisms underlying pH-dependent sugar-binding activity of human galectin-1, which is involved in cell adhesion, using spectroscopic techniques including UV resonance Raman spectroscopy. The decreased activity at acidic pH was attributed to a conformational change in the sugar-binding pocket caused by protonation of His52 (pKa 6.3) and the cation-π interaction between Trp68 and the protonated His44 (pKa 5.7). In addition, we show that the peak positions of the Raman bands of the C4=C5 stretching mode at approximately 1600 cm(-1) and the Nπ-C2-Nτ bending mode at approximately 1405 cm(-1) serve as markers of the His side-chain structure. The Raman signal was enhanced 12 fold using a vertical flow apparatus.

  15. Highly Resolved Sub-Terahertz Vibrational Spectroscopy of Biological Macromolecules and Bacteria Cells

    Science.gov (United States)

    2016-07-01

    HIGHLY RESOLVED SUB-TERAHERTZ VIBRATIONAL SPECTROSCOPY OF BIOLOGICAL MACROMOLECULES AND BACTERIA CELLS ECBC...SUBTITLE Highly Resolved Sub-Terahertz Vibrational Spectroscopy of Biological Macromolecules and Bacteria Cells 5a. CONTRACT NUMBER W911SR-14-P...22 4.3 Bacteria THz Study

  16. Exciton–vibrational coupling in the dynamics and spectroscopy of Frenkel excitons in molecular aggregates

    International Nuclear Information System (INIS)

    Schröter, M.; Ivanov, S.D.; Schulze, J.; Polyutov, S.P.; Yan, Y.; Pullerits, T.; Kühn, O.

    2015-01-01

    The influence of exciton–vibrational coupling on the optical and transport properties of molecular aggregates is an old problem that gained renewed interest in recent years. On the experimental side, various nonlinear spectroscopic techniques gave insight into the dynamics of systems as complex as photosynthetic antennae. Striking evidence was gathered that in these protein–pigment complexes quantum coherence is operative even at room temperature conditions. Investigations were triggered to understand the role of vibrational degrees of freedom, beyond that of a heat bath characterized by thermal fluctuations. This development was paralleled by theory, where efficient methods emerged, which could provide the proper frame to perform non-Markovian and non-perturbative simulations of exciton–vibrational dynamics and spectroscopy. This review summarizes the state of affairs of the theory of exciton–vibrational interaction in molecular aggregates and photosynthetic antenna complexes. The focus is put on the discussion of basic effects of exciton–vibrational interaction from the stationary and dynamics points of view. Here, the molecular dimer plays a prominent role as it permits a systematic investigation of absorption and emission spectra by numerical diagonalization of the exciton–vibrational Hamiltonian in a truncated Hilbert space. An extension to larger aggregates, having many coupled nuclear degrees of freedom, becomes possible with the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for wave packet propagation. In fact it will be shown that this method allows one to approach the limit of almost continuous spectral densities, which is usually the realm of density matrix theory. Real system–bath situations are introduced for two models, which differ in the way strongly coupled nuclear coordinates are treated, as a part of the relevant system or the bath. A rather detailed exposition of the Hierarchy Equations Of Motion (HEOM

  17. In Situ Adsorption Studies at the Solid/Liquid Interface: Characterization of Biological Surfaces and Interfaces Using Sum Frequency Generation Vibrational Spectroscopy, Atomic Force Microscopy, and Quartz Crystal Microbalance

    International Nuclear Information System (INIS)

    Phillips, D.C.

    2006-01-01

    Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and quartz crystal microbalance (QCM) have been used to study the molecular surface structure, surface topography and mechanical properties, and quantitative adsorbed amount of biological molecules at the solid-liquid interface. The molecular-level behavior of designed peptides adsorbed on hydrophobic polystyrene and hydrophilic silica substrates has been examined as a model of protein adsorption on polymeric biomaterial surfaces. Proteins are such large and complex molecules that it is difficult to identify the features in their structure that lead to adsorption and interaction with solid surfaces. Designed peptides which possess secondary structure provide simple model systems for understanding protein adsorption. Depending on the amino acid sequence of a peptide, different secondary structures (α-helix and β-sheet) can be induced at apolar (air/liquid or air/solid) interfaces. Having a well-defined secondary structure allows experiments to be carried out under controlled conditions, where it is possible to investigate the affects of peptide amino acid sequence and chain length, concentration, buffering effects, etc. on adsorbed peptide structure. The experiments presented in this dissertation demonstrate that SFG vibrational spectroscopy can be used to directly probe the interaction of adsorbing biomolecules with a surface or interface. The use of well designed model systems aided in isolation of the SFG signal of the adsorbing species, and showed that surface functional groups of the substrate are sensitive to surface adsorbates. The complementary techniques of AFM and QCM allowed for deconvolution of the effects of surface topography and coverage from the observed SFG spectra. Initial studies of biologically relevant surfaces are also presented: SFG spectroscopy was used to study the surface composition of common soil bacteria for use in bioremediation of nuclear waste

  18. In Situ Adsorption Studies at the Solid/Liquid Interface:Characterization of Biological Surfaces and Interfaces Using SumFrequency Generation Vibrational Spectroscopy, Atomic Force Microscopy,and Quartz Crystal Microbalance

    Energy Technology Data Exchange (ETDEWEB)

    Phillips, Diana Christine [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Sum frequency generation (SFG) vibrational spectroscopy, atomic force microscopy (AFM), and quartz crystal microbalance (QCM) have been used to study the molecular surface structure, surface topography and mechanical properties, and quantitative adsorbed amount of biological molecules at the solid-liquid interface. The molecular-level behavior of designed peptides adsorbed on hydrophobic polystyrene and hydrophilic silica substrates has been examined as a model of protein adsorption on polymeric biomaterial surfaces. Proteins are such large and complex molecules that it is difficult to identify the features in their structure that lead to adsorption and interaction with solid surfaces. Designed peptides which possess secondary structure provide simple model systems for understanding protein adsorption. Depending on the amino acid sequence of a peptide, different secondary structures (α-helix and β-sheet) can be induced at apolar (air/liquid or air/solid) interfaces. Having a well-defined secondary structure allows experiments to be carried out under controlled conditions, where it is possible to investigate the affects of peptide amino acid sequence and chain length, concentration, buffering effects, etc. on adsorbed peptide structure. The experiments presented in this dissertation demonstrate that SFG vibrational spectroscopy can be used to directly probe the interaction of adsorbing biomolecules with a surface or interface. The use of well designed model systems aided in isolation of the SFG signal of the adsorbing species, and showed that surface functional groups of the substrate are sensitive to surface adsorbates. The complementary techniques of AFM and QCM allowed for deconvolution of the effects of surface topography and coverage from the observed SFG spectra. Initial studies of biologically relevant surfaces are also presented: SFG spectroscopy was used to study the surface composition of common soil bacteria for use in bioremediation of nuclear waste.

  19. Developing and understanding biofluid vibrational spectroscopy: a critical review.

    Science.gov (United States)

    Baker, Matthew J; Hussain, Shawn R; Lovergne, Lila; Untereiner, Valérie; Hughes, Caryn; Lukaszewski, Roman A; Thiéfin, Gérard; Sockalingum, Ganesh D

    2016-04-07

    Vibrational spectroscopy can provide rapid, label-free, and objective analysis for the clinical domain. Spectroscopic analysis of biofluids such as blood components (e.g. serum and plasma) and others in the proximity of the diseased tissue or cell (e.g. bile, urine, and sputum) offers non-invasive diagnostic/monitoring possibilities for future healthcare that are capable of rapid diagnosis of diseases via specific spectral markers or signatures. Biofluids offer an ideal diagnostic medium due to their ease and low cost of collection and daily use in clinical biology. Due to the low risk and invasiveness of their collection they are widely welcomed by patients as a diagnostic medium. This review underscores recent research within the field of biofluid spectroscopy and its use in myriad pathologies such as cancer and infectious diseases. It highlights current progresses, advents, and pitfalls within the field and discusses future spectroscopic clinical potentials for diagnostics. The requirements and issues surrounding clinical translation are also considered.

  20. Sub-THz spectroscopic characterization of vibrational modes in artificially designed DNA monocrystal

    International Nuclear Information System (INIS)

    Sizov, Igor; Rahman, Masudur; Gelmont, Boris; Norton, Michael L.; Globus, Tatiana

    2013-01-01

    Highlights: • Sub-THz spectroscopy is used to characterize artificially designed DNA monocrystal. • Results are obtained using a novel near field, RT, frequency domain spectrometer. • Narrow resonances of 0.1 cm −1 width in absorption spectra of crystal are observed. • Signature measured between 310 and 490 GHz is reproducible and well resolved. • Absorption pattern is explained in part by simulation results from dsDNA fragment. - Abstract: Sub-terahertz (sub-THz) vibrational spectroscopy is a new spectroscopic branch for characterizing biological macromolecules. In this work, highly resolved sub-THz resonance spectroscopy is used for characterizing engineered molecular structures, an artificially designed DNA monocrystal, built from a short DNA sequence. Using a recently developed frequency domain spectroscopic instrument operating at room temperature with high spectral and spatial resolution, we demonstrated very intense and specific spectral lines from a DNA crystal in general agreement with a computational molecular dynamics (MD) simulation of a short double stranded DNA fragment. The spectroscopic signature measured in the frequency range between 310 and 490 GHz is rich in well resolved and reproducible spectral features thus demonstrating the capability of THz resonance spectroscopy to be used for characterizing custom macromolecules and structures designed and implemented via nanotechnology for a wide variety of application domains. Analysis of MD simulation indicates that intense and narrow vibrational modes with atomic movements perpendicular (transverse) and parallel (longitudinal) to the long DNA axis coexist in dsDNA, with much higher contribution from longitudinal vibrations

  1. Vibrational Spectroscopy as a Promising Toolbox for Analyzing Functionalized Ceramic Membranes.

    Science.gov (United States)

    Kiefer, Johannes; Bartels, Julia; Kroll, Stephen; Rezwan, Kurosch

    2018-01-01

    Ceramic materials find use in many fields including the life sciences and environmental engineering. For example, ceramic membranes have shown to be promising filters for water treatment and virus retention. The analysis of such materials, however, remains challenging. In the present study, the potential of three vibrational spectroscopic methods for characterizing functionalized ceramic membranes for water treatment is evaluated. For this purpose, Raman scattering, infrared (IR) absorption, and solvent infrared spectroscopy (SIRS) were employed. The data were analyzed with respect to spectral changes as well as using principal component analysis (PCA). The Raman spectra allow an unambiguous discrimination of the sample types. The IR spectra do not change systematically with functionalization state of the material. Solvent infrared spectroscopy allows a systematic distinction and enables studying the molecular interactions between the membrane surface and the solvent.

  2. Application of fluorescent and vibration spectroscopy for septic serum human albumin structure deformation during pathology

    Science.gov (United States)

    Zyubin, A.; Konstantinova, E.; Slezhkin, V.; Matveeva, K.; Samusev, I.; Bryukhanov, V.

    2017-12-01

    In this paper we perform results of conformational analysis of septic human serum albumin (HSA) carried out by Raman spectroscopy (RS), infrared (IR) spectroscopy and fluorescent spectroscopy. The main vibrational groups were identified and analyzed for septic HSA and its health control. Comparison between Raman and IR results were done. Fluorescent spectral changes of Trp-214 group were analyzed. Application of Raman, IR spectroscopy, fluorescent spectroscopy for conformational changes study of HSA during pathology were shown.

  3. Sum Frequency Generation Vibrational Spectroscopy of Colloidal Platinum Nanoparticle Catalysts: Disordering versus Removal of Organic Capping

    KAUST Repository

    Krier, James M.; Michalak, William D.; Baker, L. Robert; An, Kwangjin; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2012-01-01

    Recent work with nanoparticle catalysts shows that size and shape control on the nanometer scale influences reaction rate and selectivity. Sum frequency generation (SFG) vibrational spectroscopy is a powerful tool for studying heterogeneous

  4. Towards vibrational spectroscopy on surface-attached colloids performed with a quartz crystal microbalance

    Directory of Open Access Journals (Sweden)

    Diethelm Johannsmann

    2016-12-01

    Full Text Available Colloidal spheres attached to a quartz crystal microbalance (QCM produce the so-called “coupled resonances”. They are resonators of their own, characterized by a particle resonance frequency, a resonance bandwidth, and a modal mass. When the frequency of the main resonator comes close to the frequency of the coupled resonance, the bandwidth goes through a maximum. A coupled resonance can be viewed as an absorption line in acoustic shear-wave spectroscopy. The known concepts from spectroscopy apply. This includes the mode assignment problem, selection rules, and the oscillator strength. In this work, the mode assignment problem was addressed with Finite Element calculations. These reveal that a rigid sphere in contact with a QCM displays two modes of vibration, termed “slipping” and “rocking”. In the slipping mode, the sphere rotates about its center; it exerts a tangential force onto the resonator surface at the point of contact. In the rocking mode, the sphere rotates about the point of contact; it exerts a torque onto the substrate. In liquids, both axes of rotation are slightly displaced from their ideal positions. Characteristic for spectroscopy, the two modes do not couple to the mechanical excitation equally well. The degree of coupling is quantified by an oscillator strength. Because the rocking mode mostly exerts a torque (rather than a tangential force, its coupling to the resonator's tangential motion is weak; the oscillator strength consequently is small. Recent experiments on surface-adsorbed colloidal spheres can be explained by the mode of vibration being of the rocking type. Keywords: Quartz crystal microbalance, Coupled resonance, Biocolloids, Adsorption

  5. Two-Photon Vibrational Spectroscopy using local optical fields of gold and silver nanostructures

    Science.gov (United States)

    Kneipp, Katrin; Kneipp, Janina; Kneipp, Harald

    2007-03-01

    Spectroscopic effects can be strongly affected when they take place in the immediate vicinity of metal nanostructures due to coupling to surface plasmons. We introduce a new approach that suggests highly efficient two-photon labels as well as two-photon vibrational spectroscopy for non-destructive chemical probing. The underlying spectroscopic effect is the incoherent inelastic scattering of two photons on the vibrational quantum states performed in the enhanced local optical fields of gold nanoparticles, surface enhanced hyper Raman scattering (SEHRS). We infer effective two-photon cross sections for SEHRS on the order of 10^5 GM, similar or higher than the best known cross sections for two-photon fluorescence. SEHRS combines the advantages of two-photon spectroscopy with the structural information of vibrational spectroscopy, and the high sensitivity and nanometer-scale local confinement of plasmonics-based spectroscopy.

  6. Spectroscopy of vibrationally hot molecules: Hydrogen cyanide and acetylene

    International Nuclear Information System (INIS)

    Jonas, D.M.

    1992-01-01

    An efficient formula for calculating nuclear spin statistical weights is presented. New experimental methods to distinguish electric and magnetic multipole transitions are proposed and used to prove that the formaldehyde A - X 0-0 transition is a magnetic dipole transition. HIgh resolution vacuum ultraviolet studies of the A → X fluorescence excitation spectrum of hydrogen cyanide (HCN) have: (i) determined that only the (0,1,0) vibrational level of the HCN A-state has a sufficiently long fluorescence lifetime to be suitable for Stimulated Emission Pumping (SEP) studies; and (ii) measured the electric dipole moment of the A-state. Several transitions in the hydrogen cyanide A → X SEP spectrum are shown to be due to the axis-switching mechanism. From a Franck-Condon plot of the intensities and a comparison between sums of predicted rotational constants and sums of observed rotational constants, all of the remaining transitions in the SEP spectrum can be securly assigned. Two weak resonances; a 2:3 CH:CN stretch Fermi resonance and a 6:2 bend:CN stretch resonance appear in the SEP spectrum. Excitation of the CH stretching vibration is predicted and shown to be entirely absent, apart from resonances, in the HCN SEP spectrum. A → X SEP spectra of acetylene (HCCH) near E VIB = 7,000 cm -1 display a wealth of strong and fully assignable anharmonic resonances and forbidden rotational transitions. It is proved that Darling-Dennison resonance between the cis and trans bending vibrations is the crucial first step in a series of anharmonic resonances which can transfer nearly all the vibrational energy out of the initial CC stretch/trans-bend excitation at high vibrational energy. Secondary steps in the vibrational energy flow are vibrational-l-resonance and the '2345' Fermi resonance. For short times, the vibrational energy redistribution obeys very restrictive rules

  7. Structural determination of some uranyl compounds by vibrational spectroscopy

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1990-07-01

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  8. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

    International Nuclear Information System (INIS)

    Mandal, Aritra; Tokmakoff, Andrei

    2015-01-01

    We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm −1 . We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions

  9. Vibration characterization procedure of piezoelectric ceramic parameters

    Directory of Open Access Journals (Sweden)

    Meyer Yann

    2015-01-01

    Full Text Available To integrate new functionalities inside the mechanical structures for active vibration control, mechatronic, energy harvesting or fatigue management, it is necessary to developp a real fully distributed set of transducers and to include them at the heart of composite materials. To reach this goal, it is absolutely necessary to limit the cost of the numerous transducing elements with respect to the global system cost and, in the same time, to well-know the electromechanical behavior of theses transducers in order to well-design the system controller. In this paper, an experimental non-destructive procedure based on the analysis of anti-resonance and resonance frequencies of the transducers is proposed for determining the material coefficients of interest. This measurement process is applied to low-cost thin disks made of piezoceramics.

  10. Observation of the low frequency vibrational modes of bacteriophage M13 in water by Raman spectroscopy

    Directory of Open Access Journals (Sweden)

    Tsen Shaw-Wei D

    2006-09-01

    Full Text Available Abstract Background Recently, a technique which departs radically from conventional approaches has been proposed. This novel technique utilizes biological objects such as viruses as nano-templates for the fabrication of nanostructure elements. For example, rod-shaped viruses such as the M13 phage and tobacco mosaic virus have been successfully used as biological templates for the synthesis of semiconductor and metallic nanowires. Results and discussion Low wave number (≤ 20 cm-1 acoustic vibrations of the M13 phage have been studied using Raman spectroscopy. The experimental results are compared with theoretical calculations based on an elastic continuum model and appropriate Raman selection rules derived from a bond polarizability model. The observed Raman mode has been shown to belong to one of the Raman-active axial torsion modes of the M13 phage protein coat. Conclusion It is expected that the detection and characterization of this low frequency vibrational mode can be used for applications in nanotechnology such as for monitoring the process of virus functionalization and self-assembly. For example, the differences in Raman spectra can be used to monitor the coating of virus with some other materials and nano-assembly process, such as attaching a carbon nanotube or quantum dots.

  11. Coadsorption and reaction of H2 and CO on Raney nickel: Neutron vibrational spectroscopy

    International Nuclear Information System (INIS)

    Kelley, R.D.; Kernforschungsanlage Juelich G.m.b.H.

    1983-01-01

    Neutron vibration spectroscopy is used to study the adsorption and reaction of H 2 and Co on a catalytic nickel surface. The sample was first exposed to H 2 and than to CO. At low temperatures there is no change of vibrational modes of H in the three-fold site; at a higher temperature changes occur. Some conclusions are drawn on the reaction product. (G.Q.)

  12. Proceedings of the national conference on exploring the frontiers of vibrational spectroscopy: abstracts

    International Nuclear Information System (INIS)

    2011-01-01

    Spectroscopy has played and is playing a very important role as it is one of the most efficient methods of molecular structure studies with the help of which direct information about the chemical compounds can be obtained. Spectroscopy has its contribution in a number of branches in areas such as medicine, industry, environment, agriculture, power, construction, forensic analysis (both criminal and civil cases), etc., where it has revolutionized the very face of these sectors. Vibrational spectroscopic (Infrared and Raman) techniques have demonstrated potential to provide non-destructive, rapid clinically relevant diagnostic information. Raman and infrared spectroscopy enable the biochemical signatures from biological tissues to be extracted and analyzed there by advancing the treatment of cancer. Advancement in instrumentation has allowed the development of numerous infrared and Raman spectroscopic methods. Infrared spectroscopy is tremendously used in the fields of pharmaceuticals. medical diagnostics food and agrochemical quality control, and combustion research. Raman spectroscopy is used in condensed matter physics, biomedicinal fields for tissue analysis and chemistry to study vibrational, rotational, and other low-frequency modes in a system. Keeping in mind the fast development: in the Spectroscopy, we have planned to organize a national level conference for 2 days on 'Exploring the Frontiers of Vibrational Spectroscopy' to bring out the tremendous potential of various Spectroscopic techniques available at the global level. Papers relevant to INIS are indexed separately

  13. Polymorph characterization of active pharmaceutical ingredients (APIs) using low-frequency Raman spectroscopy.

    Science.gov (United States)

    Larkin, Peter J; Dabros, Marta; Sarsfield, Beth; Chan, Eric; Carriere, James T; Smith, Brian C

    2014-01-01

    Polymorph detection, identification, and quantitation in crystalline materials are of great importance to the pharmaceutical industry. Vibrational spectroscopic techniques used for this purpose include Fourier transform mid-infrared (FT-MIR) spectroscopy, Fourier transform near-infrared (FT-NIR) spectroscopy, Raman spectroscopy, and terahertz (THz) and far-infrared (FIR) spectroscopy. Typically, the fundamental molecular vibrations accessed using high-frequency Raman and MIR spectroscopy or the overtone and combination of bands in the NIR spectra are used to monitor the solid-state forms of active pharmaceutical ingredients (APIs). The local environmental sensitivity of the fundamental molecular vibrations provides an indirect probe of the long-range order in molecular crystals. However, low-frequency vibrational spectroscopy provides access to the lattice vibrations of molecular crystals and, hence, has the potential to more directly probe intermolecular interactions in the solid state. Recent advances in filter technology enable high-quality, low-frequency Raman spectra to be acquired using a single-stage spectrograph. This innovation enables the cost-effective collection of high-quality Raman spectra in the 200-10 cm(-1) region. In this study, we demonstrate the potential of low-frequency Raman spectroscopy for the polymorphic characterization of APIs. This approach provides several benefits over existing techniques, including ease of sampling and more intense, information-rich band structures that can potentially discriminate among crystalline forms. An improved understanding of the relationship between the crystalline structure and the low-frequency vibrational spectrum is needed for the more widespread use of the technique.

  14. Positron spectroscopy for materials characterization

    International Nuclear Information System (INIS)

    Schultz, P.J.; Snead, C.L. Jr.

    1988-01-01

    One of the more active areas of research on materials involves the observation and characterization of defects. The discovery of positron localization in vacancy-type defects in solids in the 1960's initiated a vast number of experimental and theoretical investigations which continue to this day. Traditional positron annihilation spectroscopic techniques, including lifetime studies, angular correlation, and Doppler broadening of annihilation radiation, are still being applied to new problems in the bulk properties of simple metals and their alloys. In addition new techniques based on tunable sources of monoenergetic positron beams have, in the last 5 years, expanded the horizons to studies of surfaces, thin films, and interfaces. In the present paper we briefly review these experimental techniques, illustrating with some of the important accomplishments of the field. 40 refs., 19 figs

  15. The pink pigment prodigiosin: Vibrational spectroscopy and DFT calculations

    Czech Academy of Sciences Publication Activity Database

    Jehlička, J.; Němec, I.; Varnali, T.; Culka, A.; Svatoš, A.; Frank, Otakar; Oren, A.; Edwards, G.M.

    2016-01-01

    Roč. 134, NOV 2016 (2016), s. 234-243 ISSN 0143-7208 Institutional support: RVO:61388955 Keywords : prodigiosin * serratia marcescens * raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 3.473, year: 2016

  16. Vibrational Spectroscopy of the CCl[subscript 4] v[subscript 1] Mode: Theoretical Prediction of Isotopic Effects

    Science.gov (United States)

    Gaynor, James D.; Wetterer, Anna M.; Cochran, Rea M.; Valente, Edward J.; Mayer, Steven G.

    2015-01-01

    Raman spectroscopy is a powerful experimental technique, yet it is often missing from the undergraduate physical chemistry laboratory curriculum. Tetrachloromethane (CCl[subscript 4]) is the ideal molecule for an introductory vibrational spectroscopy experiment and the symmetric stretch vibration contains fine structure due to isotopic variations…

  17. Vibrational and electronic spectroscopy of ion-implantation-induced defects in fused silica and crystalline quartz

    International Nuclear Information System (INIS)

    Arnold, G.W.

    1978-01-01

    Defects produced by implantation of various atomic species in fused and crystalline SiO 2 were studied using infrared reflection spectroscopy (IRS) with UV-visible spectroscopy. We observe a new vibrational band at 830 cm -1 which is tentatively associated with the creation of two nonbridging O atoms in SiO 4 units. Numerous chemical effects were also observed, including evidence for chemical incorporation of Li and anomalously large O-vacancy production for Al + , B + and Si + implantation

  18. Design, simulation, fabrication, and characterization of MEMS vibration energy harvesters

    Science.gov (United States)

    Oxaal, John

    Energy harvesting from ambient sources has been a longtime goal for microsystem engineers. The energy available from ambient sources is substantial and could be used to power wireless micro devices, making them fully autonomous. Self-powered wireless sensors could have many applications in for autonomous monitoring of residential, commercial, industrial, geological, or biological environments. Ambient vibrations are of particular interest for energy harvesting as they are ubiquitous and have ample kinetic energy. In this work a MEMS device for vibration energy harvesting using a variable capacitor structure is presented. The nonlinear electromechanical dynamics of a gap-closing type structure is experimentally studied. Important experimental considerations such as the importance of reducing off-axis vibration during testing, characterization methods, dust contamination, and the effect of grounding on parasitic capacitance are discussed. A comprehensive physics based model is developed and validated with two different microfabricated devices. To achieve maximal power, devices with high aspect ratio electrodes and a novel two-level stopper system are designed and fabricated. The maximum achieved power from the MEMS device when driven by sinusoidal vibrations was 3.38 muW. Vibrations from HVAC air ducts, which have a primary frequency of 65 Hz and amplitude of 155 mgrms, are targeted as the vibration source and devices are designed for maximal power harvesting potential at those conditions. Harvesting from the air ducts, the devices reached 118 nW of power. When normalized to the operating conditions, the best figure of merit of the devices tested was an order of magnitude above state-of-the-art of the devices (1.24E-6).

  19. Study of cancer cell lines with Fourier transform infrared (FTIR)/vibrational absorption (VA) spectroscopy

    DEFF Research Database (Denmark)

    Uceda Otero, E. P.; Eliel, G. S. N.; Fonseca, E. J. S.

    2013-01-01

    In this work we have used Fourier transform infrared (FTIR) / vibrational absorption (VA) spectroscopy to study two cancer cell lines: the Henrietta Lacks (HeLa) human cervix carcinoma and 5637 human bladder carcinoma cell lines. Our goal is to experimentally investigate biochemical changes...

  20. Vibrational spectroscopy and intramolecular energy transfer in isocyanic acid (HNCO)

    International Nuclear Information System (INIS)

    Coffey, M.J.; Berghout, H.L.; Woods, E. III; Crim, F.F.

    1999-01-01

    Room temperature photoacoustic spectra in the region of the first through the fourth overtones (2ν 1 to 5ν 1 ) and free-jet action spectra of the second through the fourth overtones (3ν 1 to 5ν 1 ) of the N - H stretching vibration permit analysis of the vibrational and rotational structure of HNCO. The analysis identifies the strong intramolecular couplings that control the early stages of intramolecular vibrational energy redistribution (IVR) and gives the interaction matrix elements between the zero-order N - H stretching states and the other zero-order states with which they interact. The experimentally determined couplings and zero-order state separations are consistent with ab initio calculations of East, Johnson, and Allen [J. Chem. Phys. 98, 1299 (1993)], and comparison with the calculation identifies the coupled states and likely interactions. The states most strongly coupled to the pure N - H stretching zero-order states are ones with a quantum of N - H stretching excitation (ν 1 ) replaced by different combinations of N - C - O asymmetric or symmetric stretching excitation (ν 2 or ν 3 ) and trans-bending excitation (ν 4 ). The two strongest couplings of the nν 1 state are to the states (n-1)ν 1 +ν 2 +ν 4 and (n-1)ν 1 +ν 3 +2ν 4 , and sequential couplings through a series of low order resonances potentially play a role. The analysis shows that if the pure N - H stretch zero-order state were excited, energy would initially flow out of that mode into the strongly coupled mode in 100 fs to 700 fs, depending on the level of initial excitation. copyright 1999 American Institute of Physics

  1. Chirp effects on impulsive vibrational spectroscopy: a multimode perspective.

    Science.gov (United States)

    Wand, Amir; Kallush, Shimshon; Shoshanim, Ofir; Bismuth, Oshrat; Kosloff, Ronnie; Ruhman, Sanford

    2010-03-07

    The well-documented propensity of negatively-chirped pulses to enhance resonant impulsive Raman scattering has been rationalized in terms of a one pulse pump-dump sequence which "follows" the evolution of the excited molecules and dumps them back at highly displaced configurations. The aim of this study was to extend the understanding of this effect to molecules with many displaced vibrational modes in the presence of condensed surroundings. In particular, to define an optimally chirped pulse, to investigate what exactly it "follows" and to discover how this depends on the molecule under study. To this end, linear chirp effects on vibrational coherences in poly-atomics are investigated experimentally and theoretically. Chirped pump-impulsive probe experiments are reported for Sulforhodamine-B ("Kiton Red"), Betaine-30 and Oxazine-1 in ethanol solutions with <10 fs resolution. Numerical simulations, including numerous displaced modes and electronic dephasing, are conducted to reproduce experimental results. Through semi-quantitative reproduction of experimental results in all three systems we show that the effect of group velocity dispersion (GVD) on the buildup of ground state wave-packets depends on the pulse spectrum, on the displacements of vibrational modes upon excitation, on the detuning of the excitation pulses from resonance, and on electronic dephasing rates. Akin to scenarios described for frequency-domain resonance Raman, within the small-displacement regime each mode responds to excitation chirp independently and the optimal GVD is mode-specific. Highly-displaced modes entangle the dynamics of excitation in different modes, requiring a multi-dimensional description of the response. Rapid photochemistry and ultrafast electronic dephasing narrow the window of opportunity for coherent manipulations, leading to a reduced and similar optimal chirp for different modes. Finally, non-intuitive coherent aspects of chirp "following" are predicted in the small

  2. Vibrational spectroscopy on protons and deuterons in proton conducting perovskites

    DEFF Research Database (Denmark)

    Glerup, M.; Poulsen, F.W.; Berg, R.W.

    2002-01-01

    A short review of IR-spectroscopy on protons in perovskite structure oxides is given. The nature of possible proton sites, libration and combination tones and degree of hydrogen bonding is emphasised. Three new spectroscopic experiments and/or interpretations are presented. An IR-microscopy exper......A short review of IR-spectroscopy on protons in perovskite structure oxides is given. The nature of possible proton sites, libration and combination tones and degree of hydrogen bonding is emphasised. Three new spectroscopic experiments and/or interpretations are presented. An IR...

  3. Characterization of the quasi-one-dimensional compounds δ-(EDT-TTF-CONMe{sub 2}){sub 2}X, X=AsF{sub 6} and Br by vibrational spectroscopy and density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Peterseim, Tobias; Dressel, Martin [1. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, 70550 Stuttgart (Germany); Antal, Ágnes [1. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, 70550 Stuttgart (Germany); Institute of Condensed Matter Physics, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland); Batail, Patrick [Laboratoire MOLTECH, UMR 6200 CNRS-Université d' Angers, Bt. K, UFR Sciences, 2 Boulevard Lavoisier, F-49045 Angers (France); Drichko, Natalia [1. Physikalisches Institut, Universität Stuttgart, Pfaffenwaldring 57, 70550 Stuttgart (Germany); Department of Physics and Astronomy, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

    2014-02-14

    We have investigated the infrared spectra of the quarter-filled charge-ordered insulators δ-(EDT-TTF-CONMe{sub 2}){sub 2}X (X= AsF{sub 6}, Br) along all three crystallographic directions in the temperature range from 300 to 10 K. DFT-assisted normal mode analysis of the neutral and ionic EDT-TTF-CONMe{sub 2} molecule allows us to assign the experimentally observed intramolecular modes and to obtain relevant information on the charge ordering and intramolecular interactions. From frequencies of charge-sensitive vibrations we deduce that the charge-ordered state is already present at room temperature and does not change on cooling, in agreement with previous NMR measurements. The spectra taken along the stacking direction clearly show features of vibrational overtones excited due to the anharmonic electronic molecule potential caused by the large charge disproportionation between the molecular sites. The shift of certain vibrational modes indicates the onset of the structural transition below 200 K.

  4. Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Paulo B. [Univ. of California, Berkeley, CA (United States)

    1998-12-14

    Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayer are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayer at Iiquidhapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the confirmational order of surfactant monolayers.

  5. Temperature-dependent vibrational spectroscopy to study order-disorder transitions in charge transfer complexes

    Directory of Open Access Journals (Sweden)

    Rohan Isaac

    2018-02-01

    Full Text Available Charge-transfer (CT complexes are a promising class of materials for the semiconductor industry because of their versatile properties. This class of compounds shows a variety of phase transitions, which are of interest because of their potential impact on the electronic characteristics. Here temperature-dependent vibrational spectroscopy is used to study structural phase transitions in a set of organic CT complexes. Splitting and broadening of infrared-active phonons in the complex formed between pyrene and pyromellitic dianhydride (PMDA confirm the structural transition is of the order-disorder type and complement previous x-ray diffraction (XRD results. We show that this technique is a powerful tool to characterize transitions, and apply it to a range of binary CT complexes composed of polyaromatic hyrdocarbons (anthracene, perylene, phenanthrene, pyrene, and stilbene and PMDA. We extend the understanding of transitions in perylene-PMDA and pyrene-PMDA, and show that there are no order-disorder transitions present in anthracene-PMDA, stilbene-PMDA and phenanthrene-PMDA in the temperature range investigated here.

  6. Temperature-dependent vibrational spectroscopy to study order-disorder transitions in charge transfer complexes

    Science.gov (United States)

    Isaac, Rohan; Goetz, Katelyn P.; Roberts, Drew; Jurchescu, Oana D.; McNeil, L. E.

    2018-02-01

    Charge-transfer (CT) complexes are a promising class of materials for the semiconductor industry because of their versatile properties. This class of compounds shows a variety of phase transitions, which are of interest because of their potential impact on the electronic characteristics. Here temperature-dependent vibrational spectroscopy is used to study structural phase transitions in a set of organic CT complexes. Splitting and broadening of infrared-active phonons in the complex formed between pyrene and pyromellitic dianhydride (PMDA) confirm the structural transition is of the order-disorder type and complement previous x-ray diffraction (XRD) results. We show that this technique is a powerful tool to characterize transitions, and apply it to a range of binary CT complexes composed of polyaromatic hyrdocarbons (anthracene, perylene, phenanthrene, pyrene, and stilbene) and PMDA. We extend the understanding of transitions in perylene-PMDA and pyrene-PMDA, and show that there are no order-disorder transitions present in anthracene-PMDA, stilbene-PMDA and phenanthrene-PMDA in the temperature range investigated here.

  7. Structure and orientation of interfacial proteins determined by sum frequency generation vibrational spectroscopy: method and application.

    Science.gov (United States)

    Ye, Shuji; Wei, Feng; Li, Hongchun; Tian, Kangzhen; Luo, Yi

    2013-01-01

    In situ and real-time characterization of molecular structures and orientation of proteins at interfaces is essential to understand the nature of interfacial protein interaction. Such work will undoubtedly provide important clues to control biointerface in a desired manner. Sum frequency generation vibrational spectroscopy (SFG-VS) has been demonstrated to be a powerful technique to study the interfacial structures and interactions at the molecular level. This paper first systematically introduced the methods for the calculation of the Raman polarizability tensor, infrared transition dipole moment, and SFG molecular hyperpolarizability tensor elements of proteins/peptides with the secondary structures of α-helix, 310-helix, antiparallel β-sheet, and parallel β-sheet, as well as the methodology to determine the orientation of interfacial protein secondary structures using SFG amide I spectra. After that, recent progresses on the determination of protein structure and orientation at different interfaces by SFG-VS were then reviewed, which provides a molecular-level understanding of the structures and interactions of interfacial proteins, specially understanding the nature of driving force behind such interactions. Although this review has focused on analysis of amide I spectra, it will be expected to offer a basic idea for the spectral analysis of amide III SFG signals and other complicated molecular systems such as RNA and DNA. Copyright © 2013 Elsevier Inc. All rights reserved.

  8. Theoretical vibrational sum-frequency generation spectroscopy of water near lipid and surfactant monolayer interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Roy, S.; Gruenbaum, S. M.; Skinner, J. L. [Theoretical Chemistry Institute and Department of Chemistry, 1101 University Ave., University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States)

    2014-11-14

    Understanding the structure of water near cell membranes is crucial for characterizing water-mediated events such as molecular transport. To obtain structural information of water near a membrane, it is useful to have a surface-selective technique that can probe only interfacial water molecules. One such technique is vibrational sum-frequency generation (VSFG) spectroscopy. As model systems for studying membrane headgroup/water interactions, in this paper we consider lipid and surfactant monolayers on water. We adopt a theoretical approach combining molecular dynamics simulations and phase-sensitive VSFG to investigate water structure near these interfaces. Our simulated spectra are in qualitative agreement with experiments and reveal orientational ordering of interfacial water molecules near cationic, anionic, and zwitterionic interfaces. OH bonds of water molecules point toward an anionic interface leading to a positive VSFG peak, whereas the water hydrogen atoms point away from a cationic interface leading to a negative VSFG peak. Coexistence of these two interfacial water species is observed near interfaces between water and mixtures of cationic and anionic lipids, as indicated by the presence of both negative and positive peaks in their VSFG spectra. In the case of a zwitterionic interface, OH orientation is toward the interface on the average, resulting in a positive VSFG peak.

  9. Vibrational spectroscopy and structural analysis of uranium complexes

    Energy Technology Data Exchange (ETDEWEB)

    Umrejko, D.S.; Nikanovich, M.V.

    1984-12-01

    On the basis of experimental and theoretical studies of vibbrational spectra for halides, sulfates, phosphates, uranyl oxalates (and uranium) as well as for more complicated complex systems, reliable spectroscopic criteria have been established for estimation of their structural features by more simple and accessible (than direct) methods. Due to coordination to a central ion of U/sup 6/(U/sup 4/) ligands a geometry variation specific for each method of addition occurs and concomitant redistribution of the force interaction in the mentioned system as well, which directly affects the variation of their frequency characteristics and vibration modes. On this ground stable indications of particular types of coordination for mono- and polyatomic groups (including bridge-type, characteristic of polymetric structures) are pointed out in the IR absorption and Raman spectra. In the investigated structures the predominant effect of coordination on the spectral properties of complexes, as compared with other factors (for example, outer-sphere binding) is established. The presence of water molecules in an interlayer space does not tell essentially on the state of polyatomic ligands with all donor atoms bound with the uranium central atom (particularly, in binary uranyl phosphates). In the presence of free oxygen atoms the H/sub 2/O effect can lead only to some shift of the maxima of separate bands and their additional weak splitting (in uranyl sulfates).

  10. Studies on the substrate mediated vibrational excitation of CO/Si(100) by means of SFG spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Han, Xu; Lass, Kristian; Balgar, Thorsten; Hasselbrink, Eckart [Universitaet Duisburg-Essen, Fachbereich Chemie, 45117 Essen (Germany)

    2009-07-01

    Vibrational excitations of adsorbates play an important role in chemical reaction dynamics. In the past decade CO on solid surfaces was chosen as adequate model system for studying vibrational relaxation dynamics. Our work is focused on the energy dissipation of vibrationally excited CO adsorbed on a silicon surface by means of IR/Vis sum frequency generation (SFG) spectroscopy. Here we present studies on substrate mediated excitation of vibrational modes of CO on Si(100) induced by UV radiation. We suppose the observation of highly excited internal stretch vibrations of CO caused by hot electrons generated within the silicon substrate.

  11. Experimental dynamic characterizations and modelling of disk vibrations for HDDs.

    Science.gov (United States)

    Pang, Chee Khiang; Ong, Eng Hong; Guo, Guoxiao; Qian, Hua

    2008-01-01

    Currently, the rotational speed of spindle motors in HDDs (Hard-Disk Drives) are increasing to improve high data throughput and decrease rotational latency for ultra-high data transfer rates. However, the disk platters are excited to vibrate at their natural frequencies due to higher air-flow excitation as well as eccentricities and imbalances in the disk-spindle assembly. These factors contribute directly to TMR (Track Mis-Registration) which limits achievable high recording density essential for future mobile HDDs. In this paper, the natural mode shapes of an annular disk mounted on a spindle motor used in current HDDs are characterized using FEM (Finite Element Methods) analysis and verified with SLDV (Scanning Laser Doppler Vibrometer) measurements. The identified vibration frequencies and amplitudes of the disk ODS (Operating Deflection Shapes) at corresponding disk mode shapes are modelled as repeatable disturbance components for servo compensation in HDDs. Our experimental results show that the SLDV measurements are accurate in capturing static disk mode shapes without the need for intricate air-flow aero-elastic models, and the proposed disk ODS vibration model correlates well with experimental measurements from a LDV.

  12. Far-infrared vibrational modes of DNA components studied by terahertz time-domain spectroscopy

    International Nuclear Information System (INIS)

    Fischer, B M; Walther, M; Jepsen, P Uhd

    2002-01-01

    The far-infrared dielectric function of a wide range of organic molecules is dominated by vibrations involving a substantial fraction of the atoms forming the molecule and motion associated with intermolecular hydrogen bond vibrations. Due to their collective nature such modes are highly sensitive to the intra- and intermolecular structure and thus provide a unique fingerprint of the conformational state of the molecule and effects of its environment. We demonstrate the use of terahertz time-domain spectroscopy (THz-TDS) for recording the far-infrared (0.5-4.0 THz) dielectric function of the four nucleobases and corresponding nucleosides forming the building blocks of deoxyribose nucleic acid (DNA). We observe numerous distinct spectral features with large differences between the molecules in both frequency-dependent absorption coefficient and index of refraction. Assisted by results from density-functional calculations we interpret the origin of the observed resonances as vibrations of hydrogen bonds between the molecules

  13. Damage-free vibrational spectroscopy of biological materials in the electron microscope.

    Science.gov (United States)

    Rez, Peter; Aoki, Toshihiro; March, Katia; Gur, Dvir; Krivanek, Ondrej L; Dellby, Niklas; Lovejoy, Tracy C; Wolf, Sharon G; Cohen, Hagai

    2016-03-10

    Vibrational spectroscopy in the electron microscope would be transformative in the study of biological samples, provided that radiation damage could be prevented. However, electron beams typically create high-energy excitations that severely accelerate sample degradation. Here this major difficulty is overcome using an 'aloof' electron beam, positioned tens of nanometres away from the sample: high-energy excitations are suppressed, while vibrational modes of energies electron energy loss spectra from biogenic guanine crystals in their native state, resolving their characteristic C-H, N-H and C=O vibrational signatures with no observable radiation damage. The technique opens up the possibility of non-damaging compositional analyses of organic functional groups, including non-crystalline biological materials, at a spatial resolution of ∼10 nm, simultaneously combined with imaging in the electron microscope.

  14. Collective vibrational spectra of α- and γ-glycine studied by terahertz and Raman spectroscopy

    International Nuclear Information System (INIS)

    Shi Yulei; Wang Li

    2005-01-01

    Terahertz time-domain spectroscopy is used to investigate the absorption and dispersion of polycrystalline α- and γ-glycine in the spectral region 0.5-3.0 THz. The spectra exhibit distinct features in these two crystalline phases. The observed far-infrared responses are attributed to intermolecular vibrational modes mediated by hydrogen bonds. We also measure the Raman spectra of the polycrystalline and dissolved glycine in the frequency range 28-3900 cm -1 . The results show that all the vibrational modes below 200 cm -1 are nonlocalized but are of a collective (phonon-like) nature. Furthermore, the temperature dependence of the Raman spectra of α-glycine agrees with the anharmonicity mechanism of the vibrational potentials

  15. Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing.

    Science.gov (United States)

    Abraham, Baxter; Fan, Hao; Galoppini, Elena; Gundlach, Lars

    2018-03-01

    Molecular sensitization of semiconductor films is an important technology for energy and environmental applications including solar energy conversion, photocatalytic hydrogen production, and water purification. Dye-sensitized films are also scientifically complex and interesting systems with a long history of research. In most applications, photoinduced heterogeneous electron transfer (HET) at the molecule/semiconductor interface is of critical importance, and while great progress has been made in understanding HET, many open questions remain. Of particular interest is the role of combined electronic and vibrational effects and coherence of the dye during HET. The ultrafast nature of the process, the rapid intramolecular vibrational energy redistribution, and vibrational cooling present complications in the study of vibronic coupling in HET. We present the application of a time domain vibrational spectroscopy-pump-degenerate four-wave mixing (pump-DFWM)-to dye-sensitized solid-state semiconductor films. Pump-DFWM can measure Raman-active vibrational modes that are triggered by excitation of the sample with an actinic pump pulse. Modifications to the instrument for solid-state samples and its application to an anatase TiO 2 film sensitized by a Zn-porphyrin dye are discussed. We show an effective combination of experimental techniques to overcome typical challenges in measuring solid-state samples with laser spectroscopy and observe molecular vibrations following HET in a picosecond time window. The cation spectrum of the dye shows modes that can be assigned to the linker group and a mode that is localized on the Zn-phorphyrin chromophore and that is connected to photoexcitation.

  16. Vibrational Spectroscopies and Chemometry for Nondestructive Identification and Differentiation of Painting Binders

    Directory of Open Access Journals (Sweden)

    Serena Carlesi

    2017-01-01

    Full Text Available A comprehensive dataset of vibrational spectra of different natural organic binding media is presented and discussed. The binding media were applied on a glass substrate and analyzed after three months of natural ageing. The combination of Raman and FT-NIR spectroscopies allows for an improved identification of these materials as Raman technique is more informative about the skeletal vibrations, while FT-NIR spectroscopy is more sensitive to the substituents and polar groups. The experimental results are initially discussed in the framework of current spectral assignment. Then, multivariate analysis (PCA is applied leading to differentiation among the samples. The two major principal components allow for a complete separation of the different classes of organic materials. Further differentiation within the same class is possible thanks to the secondary components. The loadings obtained from PCA are discussed on the basis of the spectral assignment leading to clear understanding of the physical basis of this differentiation process.

  17. Vibrational spectroscopy of the borate mineral kotoite Mg₃(BO₃)₂.

    Science.gov (United States)

    Frost, Ray L; Xi, Yunfei

    2013-02-15

    Vibrational spectroscopy has been used to assess the structure of kotoite a borate mineral of magnesium which is isostructural with jimboite. The mineral is orthorhombic with point group: 2/m 2/m 2/m. The mineral has the potential as a new memory insulator material. The mineral has been characterised by a combination of Raman and infrared spectroscopy. The Raman spectrum is dominated by a very intense band at 835 cm(-1), assigned to the symmetric stretching mode of tetrahedral boron. Raman bands at 919, 985 and 1015 cm(-1) are attributed to the antisymmetric stretching modes of tetrahedral boron. Kotoite is strictly an hydrous borate mineral. An intense Raman band observed at 3559 cm(-1) is attributed to the stretching vibration of hydroxyl units, more likely to be associated with the borate mineral hydroxyborate. The lack of observation of water bending modes proves the absence of water in the kotoite structure. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Iron oxides characterization by Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Basurto Sanchez, R.

    1993-01-01

    In this work rust development on low carbon wire surface after the conformation process at different temperatures was studied by Moessbauer spectroscopy. The characterization was made by determining the following spectral parameters; 1) Quadrupole splitting, 2) Isomer shift, and 3) Magnetic splitting. The area quantification determined the percentage amount of three different iron oxides. These iron oxides were: a) Wustite (Fe O), b) Hematite (Fe 2 O 3 ), and c) Magnetite (Fe 3 O 4 ) which were present in the rust studied. With the results it was possible to establish the best temperature to favor the development of each of these iron oxides. (Author)

  19. Nonlinear vibrational spectroscopy of surfactants at liquid interfaces

    Science.gov (United States)

    Miranda, Paulo Barbeitas

    Surfactants are widely used to modify physical and chemical properties of interfaces. They play an important role in many technological problems. Surfactant monolayers are also of great scientific interest because they are two-dimensional systems that may exhibit a very rich phase transition behavior and can also be considered as a model system for biological interfaces. In this Thesis, we use a second-order nonlinear optical technique (Sum-Frequency Generation - SFG) to obtain vibrational spectra of surfactant monolayers at liquid/vapor and solid/liquid interfaces. The technique has several advantages: it is intrinsically surface-specific, can be applied to buried interfaces, has submonolayer sensitivity and is remarkably sensitive to the conformational order of surfactant monolayers. The first part of the Thesis is concerned with surfactant monolayers at the air/water interface (Langmuir films). Surface crystallization of an alcohol Langmuir film and of liquid alkanes are studied and their phase transition behaviors are found to be of different nature, although driven by similar intermolecular interactions. The effect of crystalline order of Langmuir monolayers on the interfacial water structure is also investigated. It is shown that water forms a well-ordered hydrogen-bonded network underneath an alcohol monolayer, in contrast to a fatty acid monolayer which induces a more disordered structure. In the latter case, ionization of the monolayer becomes more significant with increase of the water pH value, leading to an electric-field-induced ordering of interfacial water molecules. We also show that the orientation and conformation of fairly complicated molecules in a Langmuir monolayer can be completely mapped out using a combination of SFG and second harmonic generation (SHG). For a quantitative analysis of molecular orientation at an interface, local-field corrections must be included. The second part is a study of self-assembled surfactant monolayers at the

  20. Cortical activation pattern during shoulder simple versus vibration exercises: a functional near infrared spectroscopy study

    Directory of Open Access Journals (Sweden)

    Sung Ho Jang

    2017-01-01

    Full Text Available To date, the cortical effect of exercise has not been fully elucidated. Using the functional near infrared spectroscopy, we attempted to compare the cortical effect between shoulder vibration exercise and shoulder simple exercise. Eight healthy subjects were recruited for this study. Two different exercise tasks (shoulder vibration exercise using the flexible pole and shoulder simple exercise were performed using a block paradigm. We measured the values of oxygenated hemoglobin in the four regions of interest: the primary sensory-motor cortex (SM1 total, arm somatotopy, and leg and trunk somatotopy, the premotor cortex, the supplementary motor area, and the prefrontal cortex. During shoulder vibration exercise and shoulder simple exercise, cortical activation was observed in SM1 (total, arm somatotopy, and leg and trunk somatotopy, premotor cortex, supplementary motor area, and prefrontal cortex. Higher oxygenated hemoglobin values were also observed in the areas of arm somatotopy of SM1 compared with those of other regions of interest. However, no significant difference in the arm somatotopy of SM1 was observed between the two exercises. By contrast, in the leg and trunk somatotopy of SM1, shoulder vibration exercise led to a significantly higher oxy-hemoglobin value than shoulder simple exercise. These two exercises may result in cortical activation effects for the motor areas relevant to the shoulder exercise, especially in the arm somatotopy of SM1. However, shoulder vibration exercise has an additional cortical activation effect for the leg and trunk somatotopy of SM1.

  1. Cortical activation pattern during shoulder simple versus vibration exercises: a functional near infrared spectroscopy study.

    Science.gov (United States)

    Jang, Sung Ho; Yeo, Sang Seok; Lee, Seung Hyun; Jin, Sang Hyun; Lee, Mi Young

    2017-08-01

    To date, the cortical effect of exercise has not been fully elucidated. Using the functional near infrared spectroscopy, we attempted to compare the cortical effect between shoulder vibration exercise and shoulder simple exercise. Eight healthy subjects were recruited for this study. Two different exercise tasks (shoulder vibration exercise using the flexible pole and shoulder simple exercise) were performed using a block paradigm. We measured the values of oxygenated hemoglobin in the four regions of interest: the primary sensory-motor cortex (SM1 total, arm somatotopy, and leg and trunk somatotopy), the premotor cortex, the supplementary motor area, and the prefrontal cortex. During shoulder vibration exercise and shoulder simple exercise, cortical activation was observed in SM1 (total, arm somatotopy, and leg and trunk somatotopy), premotor cortex, supplementary motor area, and prefrontal cortex. Higher oxygenated hemoglobin values were also observed in the areas of arm somatotopy of SM1 compared with those of other regions of interest. However, no significant difference in the arm somatotopy of SM1 was observed between the two exercises. By contrast, in the leg and trunk somatotopy of SM1, shoulder vibration exercise led to a significantly higher oxy-hemoglobin value than shoulder simple exercise. These two exercises may result in cortical activation effects for the motor areas relevant to the shoulder exercise, especially in the arm somatotopy of SM1. However, shoulder vibration exercise has an additional cortical activation effect for the leg and trunk somatotopy of SM1.

  2. Spectroscopy

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules.......This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules....

  3. Characterization of Kevlar Using Raman Spectroscopy

    Science.gov (United States)

    Washer, Glenn; Brooks, Thomas; Saulsberry, Regor

    2007-01-01

    This paper explores the characterization of Kevlar composite materials using Raman spectroscopy. The goal of the research is to develop and understand the Raman spectrum of Kevlar materials to provide a foundation for the development of nondestructive evaluation (NDE) technologies based on the interaction of laser light with the polymer Kevlar. The paper discusses the fundamental aspects of experimental characterization of the spectrum of Kevlar, including the effects of incident wavelength, polarization and laser power. The effects of environmental exposure of Kevlar materials on certain characteristics of its Raman spectrum are explored, as well as the effects of applied stress. This data may provide a foundation for the development of NDE technologies intended to detect the in-situ deterioration of Kevlar materials used for engineering applications that can later be extended to other materials such as carbon fiber composites.

  4. Vibrational spectroscopy of photosensitizer dyes for organic solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Perez Leon, C.

    2005-11-18

    Ruthenium(II) complexes containing polypyridyl ligands are intensely investigated as potential photosensitizers in organic solar cells. Of particular interest is their use in dye-sensitized solar cells based on nanocrystalline films of TiO{sub 2}. Functional groups of the dye allow for efficient anchoring on the semiconductor surface and promote the electronic communication between the donor orbital of the dye and the conduction band of the semiconductor. In the present work a new dye, [Ru(dcbpyH{sub 2}){sub 2}(bpy-TPA{sub 2})](PF6{sub )2}, and the well known (Bu{sub 4}N){sub 2}[Ru(dcbpyH){sub 2}(NCS){sub 2}] complex were spectroscopically characterized. The electronic transitions of both dyes showed solvatochromic shifts due to specific interactions of the ligands with the solvent molecules. The surface-enhanced Raman (SER) spectra of the dyes dissolved in water, ethanol, and acetonitrile were measured in silver and gold colloidal solutions. The results demonstrate that the dyes were adsorbed on the metallic nanoparticles in different ways for different solvents. It was also found that in the gold colloid, the aqueous solutions of both dyes did not produce any SERS signal, whereas in ethanolic solution the SERS effect was very weak. Deprotonation, H-bonding, and donor-acceptor interactions seem to determine these different behaviors. Our results indicate the important role of the charge transfer mechanism in SERS. The adsorption of the dye on two different TiO{sub 2} substrates, anatase paste films and anatase nanopowder, was also studied to clarify the role of the carboxylate groups in the anchoring process of the dyes on the semiconductor surface. The recorded spectra indicate a strong dependence of the anchoring configuration on the morphology of the semiconductor. (orig.)

  5. Investigation of organometallic reaction mechanisms with one and two dimensional vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cahoon, James Francis [Univ. of California, Berkeley, CA (United States)

    2008-12-01

    One and two dimensional time-resolved vibrational spectroscopy has been used to investigate the elementary reactions of several prototypical organometallic complexes in room temperature solution. The electron transfer and ligand substitution reactions of photogenerated 17-electron organometallic radicals CpW(CO)3 and CpFe(CO)2 have been examined with one dimensional spectroscopy on the picosecond through microsecond time-scales, revealing the importance of caging effects and odd-electron intermediates in these reactions. Similarly, an investigation of the photophysics of the simple Fischer carbene complex Cr(CO)5[CMe(OMe)] showed that this class of molecule undergoes an unusual molecular rearrangement on the picosecond time-scale, briefly forming a metal-ketene complex. Although time-resolved spectroscopy has long been used for these types of photoinitiated reactions, the advent of two dimensional vibrational spectroscopy (2D-IR) opens the possibility to examine the ultrafast dynamics of molecules under thermal equilibrium conditions. Using this method, the picosecond fluxional rearrangements of the model metal carbonyl Fe(CO)5 have been examined, revealing the mechanism, time-scale, and transition state of the fluxional reaction. The success of this experiment demonstrates that 2D-IR is a powerful technique to examine the thermally-driven, ultrafast rearrangements of organometallic molecules in solution.

  6. Vibrational emission analysis of the CN molecules in laser-induced breakdown spectroscopy of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fernández-Bravo, Ángel; Delgado, Tomás; Lucena, Patricia; Laserna, J. Javier, E-mail: laserna@uma.es

    2013-11-01

    Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C{sub 2} Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B{sup 2}Σ–X{sup 2}Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material. - Highlights: • Vibrational emission of CN species in laser-induced plasmas has been investigated. • Distribution of vibrational emission of CN has been found to be time dependent. • Laser irradiance affects the vibrational distribution of the CN molecules. • Plume chemistry controls the excitation mechanisms of CN

  7. Absolute Configuration of 3-METHYLCYCLOHEXANONE by Chiral Tag Rotational Spectroscopy and Vibrational Circular Dichroism

    Science.gov (United States)

    Evangelisti, Luca; Holdren, Martin S.; Mayer, Kevin J.; Smart, Taylor; West, Channing; Pate, Brooks

    2017-06-01

    The absolute configuration of 3-methylcyclohexanone was established by chiral tag rotational spectroscopy measurements using 3-butyn-2-ol as the tag partner. This molecule was chosen because it is a benchmark measurement for vibrational circular dichroism (VCD). A comparison of the analysis approaches of chiral tag rotational spectroscopy and VCD will be presented. One important issue in chiral analysis by both methods is the conformational flexibility of the molecule being analyzed. The analysis of conformational composition of samples will be illustrated. In this case, the high spectral resolution of molecular rotational spectroscopy and potential for spectral simplification by conformational cooling in the pulsed jet expansion are advantages for chiral tag spectroscopy. The computational chemistry requirements for the two methods will also be discussed. In this case, the need to perform conformer searches for weakly bound complexes and to perform reasonably high level quantum chemistry geometry optimizations on these complexes makes the computational time requirements less favorable for chiral tag rotational spectroscopy. Finally, the issue of reliability of the determination of the absolute configuration will be considered. In this case, rotational spectroscopy offers a "gold standard" analysis method through the determination of the ^{13}C-subsitution structure of the complex between 3-methylcyclohexanone and an enantiopure sample of the 3-butyn-2-ol tag.

  8. Vibration-rotational overtones absorption of solid hydrogens using optoacoustic spectroscopy technique

    International Nuclear Information System (INIS)

    Vieira, M.M.F.

    1985-01-01

    Vibrational-rotational overtones absorption solid hydrogens (H 2 , D 2 , HD) is studied using pulsed laser piezoeletric transducer (PULPIT) optoacoustic spectroscopy is studied. A general downward shift in energy from isolated molecular energies is observed. Studying normal-hydrogen it was observed that the phonon excitations associated with double-molecular transitions are predominantly transverse-optical phonons, whereas the excitations associated with single-molecular transitions are predominantly longitudinal - optical phonons. Multiplet structures were observed for certain double transitions in parahydrogen and orthodeuterium. The HD spectrum, besides presenting the sharp zero-phonon lines and the associated phonon side bands, like H 2 and D 2 , showed also two different features. This observation was common to all the transitions involving pure rotational excitation in H 2 and D 2 , which showed broad linewidths. This, together with some other facts (fluorescence lifetime *approx*10 5 sec; weak internal vibration and lattice coupling), led to the proposition of a mechanism for the fast nonradiative relaxation in solid hydrogens, implied from some observed experimental evidences. This relaxation, due to strong coupling, would happen in two steps: the internal vibration modes would relax to the rotational modes of the molecules, and then this rotational modes would relax to the lattice vibration modes. (Author) [pt

  9. Reaction Coordinate Leading to H2 Production in [FeFe]-Hydrogenase Identified by Nuclear Resonance Vibrational Spectroscopy and Density Functional Theory.

    Science.gov (United States)

    Pelmenschikov, Vladimir; Birrell, James A; Pham, Cindy C; Mishra, Nakul; Wang, Hongxin; Sommer, Constanze; Reijerse, Edward; Richers, Casseday P; Tamasaku, Kenji; Yoda, Yoshitaka; Rauchfuss, Thomas B; Lubitz, Wolfgang; Cramer, Stephen P

    2017-11-22

    [FeFe]-hydrogenases are metalloenzymes that reversibly reduce protons to molecular hydrogen at exceptionally high rates. We have characterized the catalytically competent hydride state (H hyd ) in the [FeFe]-hydrogenases from both Chlamydomonas reinhardtii and Desulfovibrio desulfuricans using 57 Fe nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT). H/D exchange identified two Fe-H bending modes originating from the binuclear iron cofactor. DFT calculations show that these spectral features result from an iron-bound terminal hydride, and the Fe-H vibrational frequencies being highly dependent on interactions between the amine base of the catalytic cofactor with both hydride and the conserved cysteine terminating the proton transfer chain to the active site. The results indicate that H hyd is the catalytic state one step prior to H 2 formation. The observed vibrational spectrum, therefore, provides mechanistic insight into the reaction coordinate for H 2 bond formation by [FeFe]-hydrogenases.

  10. Characterization of UO2 by infrared spectroscopy

    International Nuclear Information System (INIS)

    Faeda, Kelly C.M.; Machado, Geraldo C.; Lameiras, Fernando S.

    2011-01-01

    The characterization of nuclear fuel is of great importance to minimize the effects related to burnup and temperature and to achieve stability during in-core operation. The understanding the U-O system and its thermodynamic properties has fundamental importance in nuclear industry. Many physical properties of UO 2±x depend on the ratio O / U, such as the electrical conductivity and thermal properties, as well as the diffusivities of its constituents and solutes. The U-O system presents various oxides such as UO 2±x , U 4 O 9 , U 3 O 8 , and UO 3 . The control of the O/U relation is critical to the manufacturing process of UO 2 . In this work, the infrared spectroscopy was used to identify the presence of phases in UO 2 powder samples that cannot be identified by thermogravimetry and X-ray diffraction. (author)

  11. Enantioselective silver nanoclusters: Preparation, characterization and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Farrag, Mostafa, E-mail: mostafafarrag@aun.edu.eg

    2016-09-01

    Herein, we report a new wet-synthesis method to separate some water-soluble chiral silver nanoclusters with high yield. The cluster material was obtained by the reduction of silver nitrate with NaBH{sub 4} in the presence of three ligands L-penicillamine (L-pen), D-penicillamine (D-pen) and racemic mixture of penicillamine (rac-pen), functioning as capping ligand. For characterizing all silver cluster samples, the particle size was assessed by transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) and their average chemical formula was determined from thermogravimetric analysis (TGA) and elemental analysis (EA). The particles sizes of all three clusters are 2.1 ± 0.2 nm. The optical properties of the samples were studied by four different methods: UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL) and circular dichroism (CD) spectroscopy. The spectra are dominated by the typical and intense plasmon peak at 486 nm accompanied by a small shoulder at 540 nm. Infrared spectroscopy was measured for the free ligand and protected silver nanoclusters, where the disappearance of the S-H vibrational band (2535–2570 cm{sup −1}) in the silver nanoclusters confirmed anchoring of ligand to the cluster surface through the sulfur atom. PL studies yielded the fluorescent properties of the samples. The main focus of this work, however, lies in the chirality of the particles. For all silver clusters CD spectra were recorded. While for clusters capped with one of the two enantiomers (D- or L-form) typical CD spectra were observed, no significant signals were detected for a racemic ligand mixture. Furthermore, silver clusters show quite large asymmetry factors (up to 3 × 10{sup −4}) in comparison to most other ligand protected clusters. These large factors and bands in the visible range of the spectrum suggest a strong chiral induction from the ligand to the metal core. Textural features of the

  12. Resolving fine spectral features in lattice vibrational modes using femtosecond coherent spectroscopy

    Directory of Open Access Journals (Sweden)

    A. Card

    2016-02-01

    Full Text Available We show resolution of fine spectral features within several Raman active vibrational modes in potassium titanyl phosphate (KTP crystal. Measurements are performed using a femtosecond time-domain coherent anti-Stokes Raman scattering spectroscopy technique that is capable of delivering equivalent spectral resolution of 0.1 cm−1. The Raman spectra retrieved from our measurements show several spectral components corresponding to vibrations of different symmetry with distinctly different damping rates. In particular, linewidths for unassigned optical phonon mode triplet centered at around 820 cm−1 are found to be 7.5 ± 0.2 cm−1, 9.1 ± 0.3 cm−1, and 11.2 ± 0.3 cm−1. Results of our experiments will ultimately help to design an all-solid-state source for sub-optical-wavelength waveform generation that is based on stimulated Raman scattering.

  13. Circularly polarized infrared and visible sum-frequency-generation spectroscopy: Vibrational optical activity measurement

    International Nuclear Information System (INIS)

    Cheon, Sangheon; Cho, Minhaeng

    2005-01-01

    Vibrational optical activity spectroscopies utilizing either circularly polarized ir or circularly polarized visible beams were theoretically investigated by considering the infrared and visible sum-frequency-generation (IV-SFG) schemes. In addition to the purely electric dipole-allowed chiral component of the IV-SFG susceptibility, the polarizability-electric quadrupole hyperpolarizability term also contributes to the vibrationally resonant IV-SFG susceptibility. The circular-intensity-difference signal is shown to be determined by the interferences between the all-electric dipole-allowed chiral component and the polarizability-electric-dipole or electric-dipole-electric-quadrupole Raman optical activity tensor components. The circularly polarized SFG methods are shown to be potentially useful coherent spectroscopic tools for determining absolute configurations of chiral molecules in condensed phases

  14. Characterisation of the membrane affinity of an isoniazide peptide conjugate by tensiometry, atomic force microscopy and sum-frequency vibrational spectroscopy, using a phospholipid Langmuir monolayer model.

    Science.gov (United States)

    Hill, Katalin; Pénzes, Csanád Botond; Schnöller, Donát; Horváti, Kata; Bosze, Szilvia; Hudecz, Ferenc; Keszthelyi, Tamás; Kiss, Eva

    2010-10-07

    Tensiometry, sum-frequency vibrational spectroscopy, and atomic force microscopy were employed to assess the cell penetration ability of a peptide conjugate of the antituberculotic agent isoniazide. Isoniazide was conjugated to peptide (91)SEFAYGSFVRTVSLPV(106), a functional T-cell epitope of the immunodominant 16 kDa protein of Mycobacterium tuberculosis. As a simple but versatile model of the cell membrane a phospholipid Langmuir monolayer at the liquid/air interface was used. Changes induced in the structure of the phospholipid monolayer by injection of the peptide conjugate into the subphase were followed by tensiometry and sum-frequency vibrational spectroscopy. The drug penetrated lipid films were transferred to a solid support by the Langmuir-Blodgett technique, and their structures were characterized by atomic force microscopy. Peptide conjugation was found to strongly enhance the cell penetration ability of isoniazide.

  15. Vibrational Spectroscopy of Intramolecular Hydrogen Bonds in the Infrared and Near-Infrared Regions

    DEFF Research Database (Denmark)

    Schrøder, Sidsel Dahl

    and 1,4-diaminobutane). Experimentally, the hydrogen bonds have been studied with vibrational spectroscopy in the infrared and near-infrared regions. The focus is primarily on spectra recorded in the near-infrared regions, which in these studies are dominated by O-H and N-H stretching overtones....... Overtone spectra have been recorded with intracavity laser photoacoustic laser spectroscopy and conventional long path absorption spectroscopy. Theoretically, a combination of electronic structure calculations and local mode models have been employed to guide the assignment of bands in the vibrational......,4-diaminobutane, no sign of intramolecular N-H···N hydrogen bonds were identified in the overtone spectra. However, theoretical analyzes indicate that intramolecular N-H···N hydrogen bonds are present in all three diamines if two hydrogen atoms on one of the methylene groups are substituted with triuoromethyl...

  16. Vibrational spectroscopy: a tool being developed for the noninvasive monitoring of wound healing

    Science.gov (United States)

    Crane, Nicole J.; Elster, Eric A.

    2012-01-01

    Wound care and management accounted for over 1.8 million hospital discharges in 2009. The complex nature of wound physiology involves hundreds of overlapping processes that we have only begun to understand over the past three decades. The management of wounds remains a significant challenge for inexperienced clinicians. The ensuing inflammatory response ultimately dictates the pace of wound healing and tissue regeneration. Consequently, the eventual timing of wound closure or definitive coverage is often subjective. Some wounds fail to close, or dehisce, despite the use and application of novel wound-specific treatment modalities. An understanding of the molecular environment of acute and chronic wounds throughout the wound-healing process can provide valuable insight into the mechanisms associated with the patient's outcome. Pathologic alterations of wounds are accompanied by fundamental changes in the molecular environment that can be analyzed by vibrational spectroscopy. Vibrational spectroscopy, specifically Raman and Fourier transform infrared spectroscopy, offers the capability to accurately detect and identify the various molecules that compose the extracellular matrix during wound healing in their native state. The identified changes might provide the objective markers of wound healing, which can then be integrated with clinical characteristics to guide the management of wounds.

  17. First-Principles Vibrational Electron Energy Loss Spectroscopy of β -Guanine

    Science.gov (United States)

    Radtke, G.; Taverna, D.; Lazzeri, M.; Balan, E.

    2017-07-01

    A general approach to model vibrational electron energy loss spectra obtained using an electron beam positioned away from the specimen is presented. The energy-loss probability of the fast electron is evaluated using first-principles quantum mechanical calculations (density functional theory) of the dielectric response of the specimen. The validity of the method is assessed using recently measured anhydrous β -guanine, an important molecular solid used by animals to produce structural colors. The good agreement between theory and experiments lays the basis for a quantitative interpretation of this spectroscopy in complex systems.

  18. The Fourteenth International Meeting on Time-Resolved Vibrational Spectroscopy (TRVS XIV)

    Science.gov (United States)

    2010-02-03

    conferences covering the use of advanced vibrational spectroscopy for the use of studying time-dependent molecular processes in chemistry, physics ...Netherlands a.huertaviga@uva.nl Neil Hunt Dept of  Physics , University of Strathclyde United Kingdom nhunt@phys.strath.ac Koichi Iwata Gakushuin University...Dasgupta Mark Creelman Sangdeok Shim Biochemical Reaction Dynamics, , , UC B k ler e ey 11:50 AM C W. Zinth, W. J. Schreier, J. Kubon, N. Regner, K

  19. Communication: atomic force detection of single-molecule nonlinear optical vibrational spectroscopy.

    Science.gov (United States)

    Saurabh, Prasoon; Mukamel, Shaul

    2014-04-28

    Atomic Force Microscopy (AFM) allows for a highly sensitive detection of spectroscopic signals. This has been first demonstrated for NMR of a single molecule and recently extended to stimulated Raman in the optical regime. We theoretically investigate the use of optical forces to detect time and frequency domain nonlinear optical signals. We show that, with proper phase matching, the AFM-detected signals closely resemble coherent heterodyne-detected signals. Applications are made to AFM-detected and heterodyne-detected vibrational resonances in Coherent Anti-Stokes Raman Spectroscopy (χ((3))) and sum or difference frequency generation (χ((2))).

  20. Are water simulation models consistent with steady-state and ultrafast vibrational spectroscopy experiments?

    International Nuclear Information System (INIS)

    Schmidt, J.R.; Roberts, S.T.; Loparo, J.J.; Tokmakoff, A.; Fayer, M.D.; Skinner, J.L.

    2007-01-01

    Vibrational spectroscopy can provide important information about structure and dynamics in liquids. In the case of liquid water, this is particularly true for isotopically dilute HOD/D 2 O and HOD/H 2 O systems. Infrared and Raman line shapes for these systems were measured some time ago. Very recently, ultrafast three-pulse vibrational echo experiments have been performed on these systems, which provide new, exciting, and important dynamical benchmarks for liquid water. There has been tremendous theoretical effort expended on the development of classical simulation models for liquid water. These models have been parameterized from experimental structural and thermodynamic measurements. The goal of this paper is to determine if representative simulation models are consistent with steady-state, and especially with these new ultrafast, experiments. Such a comparison provides information about the accuracy of the dynamics of these simulation models. We perform this comparison using theoretical methods developed in previous papers, and calculate the experimental observables directly, without making the Condon and cumulant approximations, and taking into account molecular rotation, vibrational relaxation, and finite excitation pulses. On the whole, the simulation models do remarkably well; perhaps the best overall agreement with experiment comes from the SPC/E model

  1. Vibrational spectroscopy for structural characterization of bioactive compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Majik, M.S.; Tilvi, S.

    for fast, nondestructive and green analysis, which is not possible to the other complementary techniques such as NMR and Mass. The technique coupled with NMR and mass can provide a strong platform for natural product analysis. This chapter presents...

  2. Structural characterization of chiral molecules using vibrational circular dichroism spectroscopy

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2006-01-01

    comparison of experimental and calculated spectra. Theoretical structures of the sample molecules were constructed and optimized using molecular mechanical force fields followed by the quantum mechanical method density functional theory (DFT). Calculations of IR absorption and VCD spectra were then carried...... out using the same DFT methods. Here, VCD has the advantage over CD that time-independent DFT calculations are sufficient. During the course of this project, the above methodology has been applied to a range of molecules. Some of them (nyasol, curcuphenol dimers and ginkgolide) are purely organic...... or as flexible as the curcuphenol dimer with 11 variable dihedral angles. This illustrates the capabilities of the method, which are primarily limited by the duration of DFT calculations. In the case of metal complexes, they have only recently become within reach of DFT, which opens new possibilities...

  3. Sum Frequency Generation Vibrational Spectroscopy of Colloidal Platinum Nanoparticle Catalysts: Disordering versus Removal of Organic Capping

    KAUST Repository

    Krier, James M.

    2012-08-23

    Recent work with nanoparticle catalysts shows that size and shape control on the nanometer scale influences reaction rate and selectivity. Sum frequency generation (SFG) vibrational spectroscopy is a powerful tool for studying heterogeneous catalysis because it enables the observation of surface intermediates during catalytic reactions. To control the size and shape of catalytic nanoparticles, an organic ligand was used as a capping agent to stabilize nanoparticles during synthesis. However, the presence of an organic capping agent presents two major challenges in SFG and catalytic reaction studies: it blocks a significant fraction of active surface sites and produces a strong signal that prevents the detection of reaction intermediates with SFG. Two methods for cleaning Pt nanoparticles capped with poly (vinylpyrrolidone) (PVP) are examined in this study: solvent cleaning and UV cleaning. Solvent cleaning leaves more PVP intact and relies on disordering with hydrogen gas to reduce the SFG signal of PVP. In contrast, UV cleaning depends on nearly complete removal of PVP to reduce SFG signal. Both UV and solvent cleaning enable the detection of reaction intermediates by SFG. However, solvent cleaning also yields nanoparticles that are stable under reaction conditions, whereas UV cleaning results in aggregation during reaction. The results of this study indicate that solvent cleaning is more advantageous for studying the effects of nanoparticle size and shape on catalytic selectivity by SFG vibrational spectroscopy. © 2012 American Chemical Society.

  4. Vibrational Spectroscopy of Chemical Species in Silicon and Silicon-Rich Nitride Thin Films

    Directory of Open Access Journals (Sweden)

    Kirill O. Bugaev

    2012-01-01

    Full Text Available Vibrational properties of hydrogenated silicon-rich nitride (SiN:H of various stoichiometry (0.6≤≤1.3 and hydrogenated amorphous silicon (a-Si:H films were studied using Raman spectroscopy and Fourier transform infrared spectroscopy. Furnace annealing during 5 hours in Ar ambient at 1130∘C and pulse laser annealing were applied to modify the structure of films. Surprisingly, after annealing with such high-thermal budget, according to the FTIR data, the nearly stoichiometric silicon nitride film contains hydrogen in the form of Si–H bonds. From analysis of the FTIR data of the Si–N bond vibrations, one can conclude that silicon nitride is partly crystallized. According to the Raman data a-Si:H films with hydrogen concentration 15% and lower contain mainly Si–H chemical species, and films with hydrogen concentration 30–35% contain mainly Si–H2 chemical species. Nanosecond pulse laser treatments lead to crystallization of the films and its dehydrogenization.

  5. Understanding and Manipulating Electrostatic Fields at the Protein-Protein Interface Using Vibrational Spectroscopy and Continuum Electrostatics Calculations.

    Science.gov (United States)

    Ritchie, Andrew W; Webb, Lauren J

    2015-11-05

    Biological function emerges in large part from the interactions of biomacromolecules in the complex and dynamic environment of the living cell. For this reason, macromolecular interactions in biological systems are now a major focus of interest throughout the biochemical and biophysical communities. The affinity and specificity of macromolecular interactions are the result of both structural and electrostatic factors. Significant advances have been made in characterizing structural features of stable protein-protein interfaces through the techniques of modern structural biology, but much less is understood about how electrostatic factors promote and stabilize specific functional macromolecular interactions over all possible choices presented to a given molecule in a crowded environment. In this Feature Article, we describe how vibrational Stark effect (VSE) spectroscopy is being applied to measure electrostatic fields at protein-protein interfaces, focusing on measurements of guanosine triphosphate (GTP)-binding proteins of the Ras superfamily binding with structurally related but functionally distinct downstream effector proteins. In VSE spectroscopy, spectral shifts of a probe oscillator's energy are related directly to that probe's local electrostatic environment. By performing this experiment repeatedly throughout a protein-protein interface, an experimental map of measured electrostatic fields generated at that interface is determined. These data can be used to rationalize selective binding of similarly structured proteins in both in vitro and in vivo environments. Furthermore, these data can be used to compare to computational predictions of electrostatic fields to explore the level of simulation detail that is necessary to accurately predict our experimental findings.

  6. Surface parameter characterization of surface vibrations in linear chains

    International Nuclear Information System (INIS)

    Majlis, N.; Selzer, S.; Puszkarski, H.; Diep-The-Hung

    1982-12-01

    We consider the vibrations of a linear monatomic chain with a complex surface potential defined by the surface pinning parameter a=Aesup(-i psi). It is found that in the case of a semi-infinite chain a is connected with the surface vibration wave number k=s+it by the exact relations: s=psi, t=lnA. We also show that the solutions found can be regarded as approximate ones (in the limit L>>1) for surface vibrations of a finite chain consisting of L atoms. (author)

  7. Characterization of Direct Piezoelectric Properties for Vibration Energy Harvesting

    Energy Technology Data Exchange (ETDEWEB)

    Yoshimura, Takeshi; Miyabuchi, Hiroki; Ashida, Atsushi; Fujimura, Norifumi [Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531 (Japan); Murakami, Syuichi, E-mail: tyoshi@pe.osakafu-u.ac.jp [Technology Research Institute of Osaka Prefecture, 2-7-1 Ayumino, Izumi, Osaka, 594-1157 (Japan)

    2011-10-29

    Direct piezoelectric effect of Pb(Zr,Ti)O{sub 3} (PZT) thin films was investigated to discuss the application of ferroelectric films to vibration energy harvesting. From the model of the piezoelectric vibration energy harvester, it was found that the figure of merit (FOM) is proportional of the square of the effective transverse piezoelectric coefficient e{sub 31,f}. The e{sub 31,f} coefficient of PZT films were measured by substrate bending method. Furthermore, it was found that the e{sub 31,f} coefficient increases with increasing strain, which is favourable for the vibration energy harvesting.

  8. Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

    Science.gov (United States)

    Wang, Hong-Fei; Gan, Wei; Lu, Rong; Rao, Yi; Wu, Bao-Hua

    Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = /, and comparison between the PNA method with the commonly used polarization intensity ratio (PIR) method is discussed. The polarization and incident angle dependencies of the SFG-VS intensity are also reviewed, in the light of how experimental arrangements can be optimized to effectively abstract crucial information from the SFG-VS experiments. The values and models of the local field factors in the molecular layers are discussed. In order to examine the validity and limitations of the bond polarizability derivative model, the general expressions for molecular hyperpolarizability tensors and their expression with the bond polarizability derivative model for C3v, C2v and C∞v molecular groups are given in the two appendixes. We show that the bond polarizability derivative model can quantitatively describe many aspects of the intensities observed in the SFG-VS spectrum of the vapour/neat liquid interfaces in different polarizations. Using the polarization analysis in SFG-VS, polarization selection rules or

  9. Two-dimensional vibrational spectroscopy of the amide I band of crystalline acetanilide: Fermi resonance, conformational substates, or vibrational self-trapping?

    Science.gov (United States)

    Edler, J.; Hamm, P.

    2003-08-01

    Two-dimensional infrared (2D-IR) spectroscopy is applied to investigate acetanilide, a molecular crystal consisting of quasi-one-dimensional hydrogen bonded peptide units. The amide-I band exhibits a double peak structure, which has been attributed to different mechanisms including vibrational self-trapping, a Fermi resonance, or the existence of two conformational substates. The 2D-IR spectrum of crystalline acetanilide is compared with that of two different molecular systems: (i) benzoylchloride, which exhibits a strong symmetric Fermi resonance and (ii) N-methylacetamide dissolved in methanol which occurs in two spectroscopically distinguishable conformations. Both 2D-IR spectra differ significantly from that of crystalline acetanilide, proving that these two alternative mechanisms cannot account for the anomalous spectroscopy of crystalline acetanilide. On the other hand, vibrational self-trapping of the amide-I band can naturally explain the 2D-IR response.

  10. Sample presentation, sources of error and future perspectives on the application of vibrational spectroscopy in the wine industry.

    Science.gov (United States)

    Cozzolino, Daniel

    2015-03-30

    Vibrational spectroscopy encompasses a number of techniques and methods including ultra-violet, visible, Fourier transform infrared or mid infrared, near infrared and Raman spectroscopy. The use and application of spectroscopy generates spectra containing hundreds of variables (absorbances at each wavenumbers or wavelengths), resulting in the production of large data sets representing the chemical and biochemical wine fingerprint. Multivariate data analysis techniques are then required to handle the large amount of data generated in order to interpret the spectra in a meaningful way in order to develop a specific application. This paper focuses on the developments of sample presentation and main sources of error when vibrational spectroscopy methods are applied in wine analysis. Recent and novel applications will be discussed as examples of these developments. © 2014 Society of Chemical Industry.

  11. Onsite vibrational characterization of DCMIX2/3 experiments

    Science.gov (United States)

    Ollé, Judit; Dubert, Diana; Gavaldà, Josefina; Laverón-Simavilla, Ana; Ruiz, Xavier; Shevtsova, Valentina

    2017-11-01

    The SODI-DCMIX thermodiffusion series experiments are part of the fluid research program carried out by the European Space Agency on board of the International Space Station (ISS). In particular, DCIMIX2/3 were conducted in the past inside the Microgravity Science Glovebox in the US Laboratory. Due to the physical nature of the processes implied, these kind of runs were very long and particularly delicate because the low vibratory limit requirements must be maintained for hours. This restrictive condition not always is achieved, therefore, an accurate surveillance of the acceleration levels along the different experiments is necessary, to ensure a correct interpretation of the experimental results. This work analyzes onsite vibrational environment of DCMIX2/3 covering the periods in which the experiments were going on. To do so, acceleration signals only coming from the es03 sensor, nearest to the experimental equipment and located in the Glovebox, were downloaded from the PIMS NASA website. To be as precise as possible the signals have always been treated minute by minute. To detect the transient disturbances along the experiments, several warnings were considered. First, 1 min RMS values, for the three acceleration components were evaluated, in time and in frequency domain. Additional information was obtained by plotting the power spectral densities of the signals, PSD, and their spectrogram with the aim of characterizing long periods of acceleration data. Due to great influence of low frequencies in this type of experiments, the Frequency Factor Index, FFI, was evaluated each minute. Complementary, the spectral entropy evolution was proposed as a fast new indicator of external perturbations. It has been found a good correlation between the spectrogram, temporal RMS and spectral entropy. Finally, a graphic representation of the points associated to the 1-min RMS values in one-third-octave frequency intervals which exceed the ISS limit curve requirements, was

  12. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

    Energy Technology Data Exchange (ETDEWEB)

    Dimitrievska, Mirjana; White, James L.; Zhou, Wei; Stavila, Vitalie; Klebanoff, Leonard E.; Udovic, Terrence J.

    2016-01-01

    The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (..alpha.., ..beta.., ..gamma.., and ..delta.. phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20-80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80-120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120-200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

  13. Vibrational properties of epitaxial Bi4Te3 films as studied by Raman spectroscopy

    Directory of Open Access Journals (Sweden)

    Hao Xu

    2015-08-01

    Full Text Available Bi4Te3, as one of the phases of the binary Bi–Te system, shares many similarities with Bi2Te3, which is known as a topological insulator and thermoelectric material. We report the micro-Raman spectroscopy study of 50 nm Bi4Te3 films on Si substrates prepared by molecular beam epitaxy. Raman spectra of Bi4Te3 films completely resolve the six predicted Raman-active phonon modes for the first time. Structural features and Raman tensors of Bi4Te3 films are introduced. According to the wavenumbers and assignments of the six eigenpeaks in the Raman spectra of Bi4Te3 films, it is found that the Raman-active phonon oscillations in Bi4Te3 films exhibit the vibrational properties of those in both Bi and Bi2Te3 films.

  14. Combined IR-Raman vs vibrational sum-frequency heterospectral correlation spectroscopy

    Science.gov (United States)

    Roy, Sandra; Beutier, Clémentine; Hore, Dennis K.

    2018-06-01

    Vibrational sum-frequency generation spectroscopy is a valuable probe of surface structure, particularly when the same molecules are present in one of the adjacent bulk solid or solution phases. As a result of the non-centrosymmetric requirement of SFG, the signal generated is a marker of the extent to which the molecules are ordered in an arrangement that breaks the up-down symmetry at the surface. In cases where the accompanying changes in the bulk are of interest in understanding and interpreting the surface structure, simultaneous analysis of the bulk IR absorption or bulk Raman scattering is helpful, and may be used in heterospectral surface-bulk two-dimensional correlation. We demonstrate that, in such cases, generating a new type of bulk spectrum that combines the IR and Raman amplitudes is a better candidate than the individual IR and Raman spectra for the purpose of correlation with the SFG signal.

  15. Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy.

    Science.gov (United States)

    Su, Yudan; Han, Hui-Ling; Cai, Qun; Wu, Qiong; Xie, Mingxiu; Chen, Daoyong; Geng, Baisong; Zhang, Yuanbo; Wang, Feng; Shen, Y R; Tian, Chuanshan

    2015-10-14

    Sum-frequency vibrational spectroscopy was employed to probe polymer contaminants on chemical vapor deposition (CVD) graphene and to study alkane and polyethylene (PE) adsorption on graphite. In comparing the spectra from the two surfaces, it was found that the contaminants on CVD graphene must be long-chain alkane or PE-like molecules. PE adsorption from solution on the honeycomb surface results in a self-assembled ordered monolayer with the C-C skeleton plane perpendicular to the surface and an adsorption free energy of ∼42 kJ/mol for PE(H(CH2CH2)nH) with n ≈ 60. Such large adsorption energy is responsible for the easy contamination of CVD graphene by impurity in the polymer during standard transfer processes. Contamination can be minimized with the use of purified polymers free of PE-like impurities.

  16. Laser-induced breakdown spectroscopy with laser irradiation resonant with vibrational transitions

    International Nuclear Information System (INIS)

    Khachatrian, Ani; Dagdigian, Paul J.

    2010-01-01

    An investigation of laser-induced breakdown spectroscopy (LIBS) of polymers, both in bulk form and spin coated on Si wafers, with laser irradiation in the mid-infrared spectral region is presented. Of particular interest is whether the LIBS signals are enhanced when the laser wavelength is resonant with a fundamental vibrational transition of the polymer. Significant increases in the LIBS signals were observed for irradiation on hydride stretch fundamental transitions, and the magnitude of the enhancement showed a strong dependence on the mode excited. The role of the substrate was investigated by comparison of results for bulk and spin-coated samples. The polymers investigated were Nylon 12 and poly(vinyl alcohol-co-ethylene).

  17. Theoretical study of sum-frequency vibrational spectroscopy on limonene surface

    International Nuclear Information System (INIS)

    Zheng, Ren-Hui; Liu, Hao; Jing, Yuan-Yuan; Wang, Bo-Yang; Shi, Qiang; Wei, Wen-Mei

    2014-01-01

    By combining molecule dynamics (MD) simulation and quantum chemistry computation, we calculate the surface sum-frequency vibrational spectroscopy (SFVS) of R-limonene molecules at the gas-liquid interface for SSP, PPP, and SPS polarization combinations. The distributions of the Euler angles are obtained using MD simulation, the ψ-distribution is between isotropic and Gaussian. Instead of the MD distributions, different analytical distributions such as the δ-function, Gaussian and isotropic distributions are applied to simulate surface SFVS. We find that different distributions significantly affect the absolute SFVS intensity and also influence on relative SFVS intensity, and the δ-function distribution should be used with caution when the orientation distribution is broad. Furthermore, the reason that the SPS signal is weak in reflected arrangement is discussed

  18. Theoretical study of sum-frequency vibrational spectroscopy on limonene surface

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Ren-Hui, E-mail: zrh@iccas.ac.cn; Liu, Hao; Jing, Yuan-Yuan; Wang, Bo-Yang; Shi, Qiang [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun, Beijing 100190 (China); Wei, Wen-Mei [Department of Chemistry, College of Basic Medicine, Anhui Medical University, Hefei, Anhui 230032 (China)

    2014-03-14

    By combining molecule dynamics (MD) simulation and quantum chemistry computation, we calculate the surface sum-frequency vibrational spectroscopy (SFVS) of R-limonene molecules at the gas-liquid interface for SSP, PPP, and SPS polarization combinations. The distributions of the Euler angles are obtained using MD simulation, the ψ-distribution is between isotropic and Gaussian. Instead of the MD distributions, different analytical distributions such as the δ-function, Gaussian and isotropic distributions are applied to simulate surface SFVS. We find that different distributions significantly affect the absolute SFVS intensity and also influence on relative SFVS intensity, and the δ-function distribution should be used with caution when the orientation distribution is broad. Furthermore, the reason that the SPS signal is weak in reflected arrangement is discussed.

  19. Detection of water and its derivatives on individual nanoparticles using vibrational electron energy-loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Crozier, Peter A., E-mail: crozier@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States); Aoki, Toshihiro [LeRoy Eyring Center for Solid State Science, Arizona State University, Tempe, AZ 85287-1704 (United States); Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States)

    2016-10-15

    Understanding the role of water, hydrate and hydroxyl species on nanoparticle surfaces and interfaces is very important in both physical and life sciences. Detecting the presence of oxygen-hydrogen species with nanometer resolution is extremely challenging at present. Here we show that the recently developed vibrational electron energy-loss spectroscopy using subnanometer focused electron beams can be employed to spectroscopically identify the local presence and variation of OH species on nanoscale surfaces. The hydrogen-oxygen fingerprint can be correlated with highly localized structural and morphological information obtained from electron imaging. Moreover, the current approach exploits the aloof beam mode of spectral acquisition which does not require direct electron irradiation of the sample thus greatly reducing beam damage to the OH bond. These findings open the door for using electron microscopy to probe local hydroxyl and hydrate species on nanoscale organic and inorganic structures. - Highlights: • High spatial resolution spectroscopic detection of water related species in nanoparticles. • Detection of OH stretch modes with vibrational EELS. • Differentiation between hydrate and hydroxide species on or on nanoparticles. • Detection of hydrate on a single 60 nm oxide nanoparticle of MgO. • Use of aloof beam EELS to minimize radiation damage.

  20. Thz Spectroscopy and DFT Modeling of Intermolecular Vibrations in Hydrophobic Amino Acids

    Science.gov (United States)

    Williams, michael R. C.; Aschaffenburg, Daniel J.; Schmuttenmaer, Charles A.

    2013-06-01

    Vibrations that involve intermolecular displacements occur in molecular crystals at frequencies in the 0.5-5 THz range (˜15-165 cm^{-1}), and these motions are direct indicators of the interaction potential between the molecules. The intermolecular potential energy surface of crystalline hydrophobic amino acids is inherently interesting simply because of the wide variety of forces (electrostatic, dipole-dipole, hydrogen-bonding, van der Waals) that are present. Furthermore, an understanding of these particular interactions is immediately relevant to important topics like protein conformation and pharmaceutical polymorphism. We measured the low-frequency absorption spectra of several polycrystalline hydrophobic amino acids using THz time-domain spectroscopy, and in addition we carried out DFT calculations using periodic boundary conditions and an exchange-correlation functional that accounts for van der Waals dispersion forces. We chose to investigate a series of similar amino acids with closely analogous unit cells (leucine, isoleucine, and allo-isoleucine, in racemic or pseudo-racemic mixtures). This allows us to consider trends in the vibrational spectra as a function of small changes in molecular arrangement and/or crystal geometry. In this way, we gain confidence that peak assignments are not based on serendipitous similarities between calculated and observed features.

  1. Vibrational spectroscopy and principal component analysis for conformational study of virus nucleic acids

    Science.gov (United States)

    Dovbeshko, G. I.; Repnytska, O. P.; Pererva, T.; Miruta, A.; Kosenkov, D.

    2004-07-01

    Conformation analysis of mutated DNA-bacteriophages (PLys-23, P23-2, P47- the numbers have been assigned by T. Pererva) induced by MS2 virus incorporated in Ecoli AB 259 Hfr 3000 has been done. Surface enhanced infrared absorption (SEIRA) spectroscopy and principal component analysis has been applied for solving this problem. The nucleic acids isolated from the mutated phages had a form of double stranded DNA with different modifications. The nucleic acid from phage P47 was undergone the structural rearrangement in the most degree. The shape and position ofthe fine structure of the Phosphate asymmetrical band at 1071cm-1 as well as the stretching OH vibration at 3370-3390 cm-1 has indicated to the appearance ofadditional OH-groups. The Z-form feature has been found in the base vibration region (1694 cm-1) and the sugar region (932 cm-1). A supposition about modification of structure of DNA by Z-fragments for P47 phage has been proposed. The P23-2 and PLys-23 phages have showed the numerous minor structural changes also. On the basis of SEIRA spectra we have determined the characteristic parameters of the marker bands of nucleic acid used for construction of principal components. Contribution of different spectral parameters of nucleic acids to principal components has been estimated.

  2. Infrared characterization of environmental samples by pulsed photothermal spectroscopy

    International Nuclear Information System (INIS)

    Seidel, W.; Foerstendorf, H.; Heise, K.H.; Nicolai, R.; Schamlott, A.; Ortega, J.M.; Glotin, F.; Prazeres, R.

    2004-01-01

    Low concentration of toxic radioactive metals in environmental samples often limits the interpretation of results of infrared studies investigating the interaction processes between the metal ions and environmental compartments. For the first time, we could show that photothermal infrared spectroscopy performed with a pulsed free electron laser can provide reliable infrared spectra throughout a distinct spectral range of interest. In this model investigation, we provide vibrational absorption spectra of a rare earth metal salt dissolved in a KBr matrix and a natural calcite sample obtained by photothermal beam deflection (PTBD) technique and FT-IR (Fourier-transform infrared) spectroscopy, respectively. General agreement was found between all spectra of the different recording techniques. Spectral deviations were observed with samples containing low concentration of the rare earth metal salt indicating a lower detection limit of the photothermal method as compared to conventional FT-IR spectroscopy. (authors)

  3. Gas Phase Vibrational Spectroscopy of Weakly Volatil Safe Taggants Using a Synchrotron Source

    Science.gov (United States)

    Cuisset, Arnaud; Hindle, Francis; Mouret, Gael; Gruet, Sebastien; Pirali, Olivier; Roy, Pascale

    2013-06-01

    The high performances of the AILES beamline of SOLEIL allow to study at medium resolution (0.5 cm^{-1}) the gas phase THz vibrational spectra of weakly volatil compounds. Between 2008 and 2010 we recorded and analyzed the THz/Far-IR spectra of phosphorous based nerve agents thanks to sufficient vapour pressures from liquid samples at room temperature. Recently, we extended these experiments towards the vibrational spectroscopy of vapour pressures from solid samples. This project is quite challenging since we target lower volatile compounds, and so requires very high sensitive spectrometers. Moreover a specially designed heated multipass-cell have been developped for the gas phase study of very weak vapor pressures. Thanks to skills acquired during initial studies and recent experiments performed on AILES with solid PAHs, we have recorded and assigned the gas phase vibrational fingerprints from the THz to the NIR spectral domain (10-4000 cm-1) of a set of targeted nitro-derivatives. The study was focused onto the para, ortho-mononitrotoluene (p-NT, o-NT), the 1,4 Dinitrobenzene (1,4 DNB), the 2,3-dimethyl-2,3-dinitrobutane (DMNB), and 2,4 and 2,6-dinitrotoluene (2,4-2,6 DNT), which are safe taggants widely used for the detection of commercial explosives. These taggants are usually added to plastic explosives in order to facilitate their vapour detection. Therefore, there is a continuous interest for their detection and identification in realistic conditions via optical methods. A first step consists in the recording of their gas phase vibrational spectra. These expected spectra focused onto molecules involved into defence and security domains are not yet available to date and will be very useful for the scientific community. This work is supported by the contract ANR-11-ASTR-035-01. A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525 I. Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O

  4. Structure determination of butylone as a new psychoactive substance using chiroptical and vibrational spectroscopies.

    Science.gov (United States)

    Spálovská, Dita; Králík, František; Kohout, Michal; Jurásek, Bronislav; Habartová, Lucie; Kuchař, Martin; Setnička, Vladimír

    2018-05-01

    Recently, there has been a worldwide substantial increase in the consumption of new psychoactive substances (NPS), compounds that mimic the structure of illicit drugs, such as amphetamines or ecstasy. The producers try to avoid the law by a slight modification of illicit structures, thereby developing dozens of temporarily legal NPS every year. The current trends in the detection and monitoring of such substances demand a fast and reliable analysis. Molecular spectroscopy represents a highly effective tool for the identification of NPS and chiroptical methods can provide further information on their 3D structure, which is the key for the determination of their biological activity. We present the first systematic study of NPS, specifically butylone, combining chiroptical and vibrational spectroscopies with ab initio calculations. According to density functional theory calculations, 6 stable lowest energy conformers of butylone were found and their molecular structure was described. For each conformer, the relative abundance based on the Boltzmann distribution was estimated, their population weighted spectra predicted and compared to the experimental results. Very good agreement between the experimental and the simulated spectra was achieved, which allowed not only the assignment of the absolute configuration, but also a precise description of the molecular structure. © 2018 Wiley Periodicals, Inc.

  5. Probing the Vibrational Spectroscopy of the Deprotonated Thymine Radical by Photodetachment and State-Selective Autodetachment Photoelectron Spectroscopy via Dipole-Bound States

    Science.gov (United States)

    Huang, Dao-Ling; Zhu, Guo-Zhu; Wang, Lai-Sheng

    2016-06-01

    Deprotonated thymine can exist in two different forms, depending on which of its two N sites is deprotonated: N1[T-H]^- or N3[T-H]^-. Here we report a photodetachment study of the N1[T-H]^- isomer cooled in a cryogenic ion trap and the observation of an excited dipole-bound state. Eighteen vibrational levels of the dipole-bound state are observed, and its vibrational ground state is found to be 238 ± 5 wn below the detachment threshold of N1[T-H]^-. The electron affinity of the deprotonated thymine radical (N1[T-H]^.) is measured accruately to be 26 322 ± 5 wn (3.2635 ± 0.0006 eV). By tuning the detachment laser to the sixteen vibrational levels of the dipole-bound state that are above the detachment threshold, highly non-Franck-Condon resonant-enhanced photoelectron spectra are obtained due to state- and mode-selective vibrational autodetachment. Much richer vibrational information is obtained for the deprotonated thymine radical from the photodetachment and resonant-enhanced photoelectron spectroscopy. Eleven fundamental vibrational frequencies in the low-frequency regime are obtained for the N1[T-H]^. radical, including the two lowest-frequency internal rotational modes of the methyl group at 70 ± 8 wn and 92 ± 5 wn. D. L. Huang, H. T. Liu, C. G. Ning, G. Z. Zhu and L. S. Wang, Chem. Sci., 6, 3129-3138 (2015)

  6. Characterization and synthesis of random acceleration vibration specifications

    NARCIS (Netherlands)

    Wijker, Jacob J; Ellenbroek, Marcellinus Hermannus Maria; de Boer, Andries; Papadrakakis, M.; Lagaros, N.D.; Plevris, V.

    2013-01-01

    Random acceleration vibration specifications for subsystems, i.e. instruments, equipment, are most times based on measurement during acoustic noise tests on system level, i.e. a spacecraft and measured by accelerometers, placed in the neighborhood of the interface between spacecraft and subsystem.

  7. Materials characterization by resonant ultrasonic spectroscopy method

    International Nuclear Information System (INIS)

    Cheong, Yong Moo; Jung, H.K.; Joo, Y.S.; Sim, C.M.

    2001-01-01

    A high temperature resonant ultrasound spectroscopy(RUS) was developed. The dynamic elastic constant of RPV weld, which has various different microstructure was determined by RUS. It was confirmed the RUS method is very sensitive to the microstructures of the material. RUS can be used to monitor the degradation of nuclear materials including neutron irradiation embrittlement through the measurement of dynamic elastic constants, elastic anisotropy, high temperature elastic constant and Q-factor

  8. Characterization of the intergrain and surface properties of Y1Ba2Cu3O7-x by Raman spectroscopy

    International Nuclear Information System (INIS)

    Erle, A.; Blumenroder, S.; Guntherodt, G.

    1989-01-01

    The intergrain region of polycrystalline YBa 2 Cu 3 O 7 - x has been identified by Raman spectroscopy as due to BaCuO 2 , which forms a coating of the grains. The oxygen concentration near the surface of single crystals (within ∼ 1000 Angstrom penetration depth of the light) is characterized by the intensity of the 590-cm - 1 oxygen vibration along the Cu-O chains

  9. Characterizing Exoplanet Habitability with Emission Spectroscopy

    Science.gov (United States)

    Robinson, Tyler

    2018-01-01

    Results from NASA’s Kepler mission and other recent exoplanet surveys have demonstrated that potentially habitable exoplanets are relatively common, especially in the case of low-mass stellar hosts. The next key question that must be addressed for such planets is whether or not these worlds are actually habitable, implying they could sustain surface liquid water. Only through investigations of the potential habitability of exoplanets and through searches for biosignatures from these planets will we be able to understand if the emergence of life is a common phenomenon in our galaxy. Emission spectroscopy for transiting exoplanets (sometimes called secondary eclipse spectroscopy) is a powerful technique that future missions will use to study the atmospheres and surfaces of worlds orbiting in the habitable zones of nearby, low-mass stars. Emission observations that span the mid-infrared wavelength range for potentially habitable exoplanets provide opportunities to detect key habitability and life signatures, and also allow observers to probe atmospheric and surface temperatures. This presentation will outline the case for using emission spectroscopy to understand if an exoplanet can sustain surface liquid water, which is believed to be a critical precursor to the origin of life.

  10. Site-Specific Characterization of Cytochrome P450cam Conformations by Infrared Spectroscopy.

    Science.gov (United States)

    Basom, Edward J; Maj, Michał; Cho, Minhaeng; Thielges, Megan C

    2016-06-21

    Conformational changes are central to protein function but challenging to characterize with both high spatial and temporal precision. The inherently fast time scale and small chromophores of infrared (IR) spectroscopy are well-suited for characterization of potentially rapidly fluctuating environments, and when frequency-resolved probes are incorporated to overcome spectral congestion, enable characterization of specific sites in proteins. We selectively incorporated p-cyanophenylalanine (CNF) as a vibrational probe at five distinct locations in the enzyme cytochrome P450cam and used IR spectroscopy to characterize the environments in substrate and/or ligand complexes reflecting those in the catalytic cycle. Molecular dynamics (MD) simulations were performed to provide a structural basis for spectral interpretation. Together the experimental and simulation data suggest that the CN frequencies are sensitive to both long-range influences, resulting from the particular location of a residue within the enzyme, as well as short-range influences from hydrogen bonding and packing interactions. The IR spectra demonstrate that the environments and effects of substrate and/or ligand binding are different at each position probed and also provide evidence that a single site can experience multiple environments. This study illustrates how IR spectroscopy, when combined with the spectral decongestion and spatial selectivity afforded by CNF incorporation, provides detailed information about protein structural changes that underlie function.

  11. Characterization of bundled and individual triple-walled carbon nanotubes by resonant Raman spectroscopy.

    Science.gov (United States)

    Hirschmann, Thomas Ch; Araujo, Paulo T; Muramatsu, Hiroyuki; Zhang, Xu; Nielsch, Kornelius; Kim, Yoong Ahm; Dresselhaus, Mildred S

    2013-03-26

    The optical characterization of bundled and individual triple-walled carbon nanotubes was studied for the first time in detail by using resonant Raman spectroscopy. In our approach, the outer tube of a triple-walled carbon nanotube system protects the two inner tubes (or equivalently the inner double-walled carbon nanotube) from external environment interactions making them a partially isolated system. Following the spectral changes and line-widths of the radial breathing modes and G-band by performing laser energy dependent Raman spectroscopy, it is possible to extract important information as regards to the electronic and vibrational properties, tube diameters, wall-to-wall distances, radial breathing mode, and G-band resonance evolutions as well as high-curvature intertube interactions in isolated double- and triple-walled carbon nanotube systems.

  12. Vibrational Surface Electron-Energy-Loss Spectroscopy Probes Confined Surface-Phonon Modes

    Directory of Open Access Journals (Sweden)

    Hugo Lourenço-Martins

    2017-12-01

    Full Text Available Recently, two reports [Krivanek et al. Nature (London 514, 209 (2014NATUAS0028-083610.1038/nature13870, Lagos et al. Nature (London 543, 529 (2017NATUAS0028-083610.1038/nature21699] have demonstrated the amazing possibility to probe vibrational excitations from nanoparticles with a spatial resolution much smaller than the corresponding free-space phonon wavelength using electron-energy-loss spectroscopy (EELS. While Lagos et al. evidenced a strong spatial and spectral modulation of the EELS signal over a nanoparticle, Krivanek et al. did not. Here, we show that discrepancies among different EELS experiments as well as their relation to optical near- and far-field optical experiments [Dai et al. Science 343, 1125 (2014SCIEAS0036-807510.1126/science.1246833] can be understood by introducing the concept of confined bright and dark surface phonon modes, whose density of states is probed by EELS. Such a concise formalism is the vibrational counterpart of the broadly used formalism for localized surface plasmons [Ouyang and Isaacson Philos. Mag. B 60, 481 (1989PMABDJ1364-281210.1080/13642818908205921, García de Abajo and Aizpurua Phys. Rev. B 56, 15873 (1997PRBMDO0163-182910.1103/PhysRevB.56.15873, García de Abajo and Kociak Phys. Rev. Lett. 100, 106804 (2008PRLTAO0031-900710.1103/PhysRevLett.100.106804, Boudarham and Kociak Phys. Rev. B 85, 245447 (2012PRBMDO1098-012110.1103/PhysRevB.85.245447]; it makes it straightforward to predict or interpret phenomena already known for localized surface plasmons such as environment-related energy shifts or the possibility of 3D mapping of the related surface charge densities [Collins et al. ACS Photonics 2, 1628 (2015APCHD52330-402210.1021/acsphotonics.5b00421].

  13. Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

    International Nuclear Information System (INIS)

    Mani, Tomoyasu; Brookhaven National Laboratory; Grills, David C.

    2017-01-01

    Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we show that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1 . IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.

  14. Three-body interactions in liquid and solid hydrogen: Evidence from vibrational spectroscopy

    Science.gov (United States)

    Hinde, Robert

    2008-03-01

    In the cryogenic low-density liquid and solid phases of H2 and D2, the H2 and D2 molecules retain good rotational and vibrational quantum numbers that characterize their internal degrees of freedom. High-resolution infrared and Raman spectroscopic experiments provide extremely sensitive probes of these degrees of freedom. We present here fully-first-principles calculations of the infrared and Raman spectra of liquid and solid H2 and D2, calculations that employ a high-quality six-dimensional coupled-cluster H2-H2 potential energy surface and quantum Monte Carlo treatments of the single-molecule translational degrees of freedom. The computed spectra agree very well with experimental results once we include three-body interactions among the molecules, interactions which we also compute using coupled-cluster quantum chemical methods. We predict the vibrational spectra of liquid and solid H2 at several temperatures and densities to provide a framework for interpreting recent experiments designed to search for superfluid behavior in small H2 droplets. We also present preliminary calculations of the spectra of mixed H2/D2 solids that show how positional disorder affects the spectral line shapes in these systems.

  15. Vibrational motions associated with primary processes in bacteriorhodopsin studied by coherent infrared emission spectroscopy.

    Science.gov (United States)

    Groma, Géza I; Colonna, Anne; Martin, Jean-Louis; Vos, Marten H

    2011-03-16

    The primary energetic processes driving the functional proton pump of bacteriorhodopsin take place in the form of complex molecular dynamic events after excitation of the retinal chromophore into the Franck-Condon state. These early events include a strong electronic polarization, skeletal stretching, and all-trans-to-13-cis isomerization upon formation of the J intermediate. The effectiveness of the photoreaction is ensured by a conical intersection between the electronic excited and ground states, providing highly nonadiabatic coupling to nuclear motions. Here, we study real-time vibrational coherences associated with these motions by analyzing light-induced infrared emission from oriented purple membranes in the 750-1400 cm(-)(1) region. The experimental technique applied is based on second-order femtosecond difference frequency generation on macroscopically ordered samples that also yield information on phase and direction of the underlying motions. Concerted use of several analysis methods resulted in the isolation and characterization of seven different vibrational modes, assigned as C-C stretches, out-of-plane methyl rocks, and hydrogen out-of-plane wags, whereas no in-plane H rock was found. Based on their lifetimes and several other criteria, we deduce that the majority of the observed modes take place on the potential energy surface of the excited electronic state. In particular, the direction sensitivity provides experimental evidence for large intermediate distortions of the retinal plane during the excited-state isomerization process. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  16. Scanning Angle Raman spectroscopy in polymer thin film characterization

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Vy H.T. [Iowa State Univ., Ames, IA (United States)

    2015-12-19

    The focus of this thesis is the application of Raman spectroscopy for the characterization of thin polymer films. Chapter 1 provides background information and motivation, including the fundamentals of Raman spectroscopy for chemical analysis, scanning angle Raman scattering and scanning angle Raman scattering for applications in thin polymer film characterization. Chapter 2 represents a published manuscript that focuses on the application of scanning angle Raman spectroscopy for the analysis of submicron thin films with a description of methodology for measuring the film thickness and location of an interface between two polymer layers. Chapter 3 provides an outlook and future directions for the work outlined in this thesis. Appendix A, contains a published manuscript that outlines the use of Raman spectroscopy to aid in the synthesis of heterogeneous catalytic systems. Appendix B and C contain published manuscripts that set a foundation for the work presented in Chapter 2.

  17. Characterization of alkali silica reaction gels using Raman spectroscopy

    International Nuclear Information System (INIS)

    Balachandran, C.; Muñoz, J.F.; Arnold, T.

    2017-01-01

    The ability of Raman spectroscopy to characterize amorphous materials makes this technique ideal to study alkali silica reaction (ASR) gels. The structure of several synthetic ASR gels was thoroughly characterized using Raman Spectroscopy. The results were validated with additional techniques such as Fourier transmission infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The Raman spectra were found to have two broad bands in the 800 to 1200 cm −1 range and the 400 to 700 cm −1 range indicating the amorphous nature of the gel. Important information regarding the silicate polymerization was deduced from both of these spectral regions. An increase in alkali content of the gels caused a depolymerization in the silicate framework which manifested in the Raman spectra as a gradual shift of predominant peaks in both regions. The trends in silicate depolymerization were in agreement with results from a NMR spectroscopy study on similar synthetic ASR gels.

  18. Theoretical study of molecular vibrations in electron momentum spectroscopy experiments on furan: An analytical versus a molecular dynamical approach

    International Nuclear Information System (INIS)

    Morini, Filippo; Deleuze, Michael S.; Watanabe, Noboru; Takahashi, Masahiko

    2015-01-01

    The influence of thermally induced nuclear dynamics (molecular vibrations) in the initial electronic ground state on the valence orbital momentum profiles of furan has been theoretically investigated using two different approaches. The first of these approaches employs the principles of Born-Oppenheimer molecular dynamics, whereas the so-called harmonic analytical quantum mechanical approach resorts to an analytical decomposition of contributions arising from quantized harmonic vibrational eigenstates. In spite of their intrinsic differences, the two approaches enable consistent insights into the electron momentum distributions inferred from new measurements employing electron momentum spectroscopy and an electron impact energy of 1.2 keV. Both approaches point out in particular an appreciable influence of a few specific molecular vibrations of A 1 symmetry on the 9a 1 momentum profile, which can be unravelled from considerations on the symmetry characteristics of orbitals and their energy spacing

  19. Spatially resolved localized vibrational mode spectroscopy of carbon in liquid encapsulated Czochralski grown gallium arsenide wafers

    International Nuclear Information System (INIS)

    Yau, Waifan.

    1988-04-01

    Substitutional carbon on an arsenic lattice site is the shallowest and one of the most dominant acceptors in semi-insulating Liquid Encapsulated Czochralski (LEC) GaAs. However, the role of this acceptor in determining the well known ''W'' shape spatial variation of neutral EL2 concentration along the diameter of a LEC wafer is not known. In this thesis, we attempt to clarify the issue of the carbon acceptor's effect on this ''W'' shaped variation by measuring spatial profiles of this acceptor along the radius of three different as-grown LEC GaAs wafers. With localized vibrational mode absorption spectroscopy, we find that the profile of the carbon acceptor is relatively constant along the radius of each wafer. Average values of concentration are 8 x 10E15 cm -3 , 1.1 x 10E15 cm -3 , and 2.2 x 10E15 cm -3 , respectively. In addition, these carbon acceptor LVM measurements indicate that a residual donor with concentration comparable to carbon exists in these wafers and it is a good candidate for the observed neutral EL2 concentration variation. 22 refs., 39 figs

  20. Structure and Dynamics of Urea/Water Mixtures Investigated by Vibrational Spectroscopy and Molecular Dynamics Simulation

    Science.gov (United States)

    Carr, J. K.; Buchanan, L. E.; Schmidt, J. R.; Zanni, M. T.; Skinner, J. L.

    2013-01-01

    Urea/water is an archetypical “biological” mixture, and is especially well known for its relevance to protein thermodynamics, as urea acts as a protein denaturant at high concentration. This behavior has given rise to an extended debate concerning urea’s influence on water structure. Based on a variety of methods and of definitions of water structure, urea has been variously described as a structure-breaker, a structure-maker, or as remarkably neutral towards water. Because of its sensitivity to microscopic structure and dynamics, vibrational spectroscopy can help resolve these debates. We report experimental and theoretical spectroscopic results for the OD stretch of HOD/H2O/urea mixtures (linear IR, 2DIR, and pump-probe anisotropy decay) and for the CO stretch of urea-D4/D2O mixtures (linear IR only). Theoretical results are obtained using existing approaches for water, and a modification of a frequency map developed for acetamide. All absorption spectra are remarkably insensitive to urea concentration, consistent with the idea that urea only very weakly perturbs water structure. Both this work and experiments by Rezus and Bakker, however, show that water’s rotational dynamics are slowed down by urea. Analysis of the simulations casts doubt on the suggestion that urea immobilizes particular doubly hydrogen bonded water molecules. PMID:23841646

  1. TERAHERTZ SPECTROSCOPY AND GLOBAL ANALYSIS OF THE BENDING VIBRATIONS OF ACETYLENE 12C2D2

    International Nuclear Information System (INIS)

    Yu Shanshan; Drouin, Brian J.; Pearson, John C.; Pickett, Herbert M.; Lattanzi, Valerio; Walters, Adam

    2009-01-01

    Two hundred and fifty-one 12 C 2 D 2 transitions have been measured in the 0.2-1.6 THz region of its ν 5 -ν 4 difference band and 202 of them were observed for the first time. The accuracy of these measurements is estimated to be ranging from 50 kHz to 100 kHz. The 12 C 2 D 2 molecules were generated under room temperature by passing 120-150 mTorr D 2 O vapor through calcium carbide (CaC 2 ) powder. A multistate analysis was carried out for the bending vibrational modes ν 4 and ν 5 of 12 C 2 D 2 , which includes the lines observed in this work and prior microwave, far-infrared and infrared data on the pure bending levels. Significantly improved molecular parameters were obtained for 12 C 2 D 2 by adding the new measurements to the old data set, which had only 10 lines with microwave measurement precision. New frequency and intensity predictions have been made based on the obtained molecular parameters. The more precise measurements and new predictions reported here will support the analyses of astronomical observations by the future high-resolution spectroscopy telescopes such as Herschel, SOFIA, and ALMA, which will work in the terahertz spectral region.

  2. Exploring Solvent Shape and Function Using - and Isomer-Selective Vibrational Spectroscopy

    Science.gov (United States)

    Johnson, Mark

    2010-06-01

    We illustrate the new types of information than can be obtained through isomer-selective ``hole-burning'' spectroscopy carried out in the vibrational manifolds of Ar-tagged cluster ions. Three examples of increasing complexity will be presented where the changes in a solute ion are correlated with different morphologies of a surrounding solvent cage. In the first, we discuss the weak coupling limit where different hydration morphologies lead to small distortions of a covalent ion. We then introduce the more interesting case of the hydrated electron, where different shapes of the water network lead to dramatic changes in the extent of delocalization in the diffuse excess electron cloud. We then turn to the most complex case involving hydration of the nitrosonium ion, where different arrangements of the same number of water molecules span the range in behavior from simple solvation to actively causing a chemical reaction. The latter results are particularly interesting as they provide a microscopic, molecular-level picture of the ``solvent coordinate'' commonly used to describe solvent mediated processes.

  3. Energy calibration issues in nuclear resonant vibrational spectroscopy: observing small spectral shifts and making fast calibrations.

    Science.gov (United States)

    Wang, Hongxin; Yoda, Yoshitaka; Dong, Weibing; Huang, Songping D

    2013-09-01

    The conventional energy calibration for nuclear resonant vibrational spectroscopy (NRVS) is usually long. Meanwhile, taking NRVS samples out of the cryostat increases the chance of sample damage, which makes it impossible to carry out an energy calibration during one NRVS measurement. In this study, by manipulating the 14.4 keV beam through the main measurement chamber without moving out the NRVS sample, two alternative calibration procedures have been proposed and established: (i) an in situ calibration procedure, which measures the main NRVS sample at stage A and the calibration sample at stage B simultaneously, and calibrates the energies for observing extremely small spectral shifts; for example, the 0.3 meV energy shift between the 100%-(57)Fe-enriched [Fe4S4Cl4](=) and 10%-(57)Fe and 90%-(54)Fe labeled [Fe4S4Cl4](=) has been well resolved; (ii) a quick-switching energy calibration procedure, which reduces each calibration time from 3-4 h to about 30 min. Although the quick-switching calibration is not in situ, it is suitable for normal NRVS measurements.

  4. Vibrational spectroscopy of H{sub 3}{sup +} - advancing into the visible spectral region

    Energy Technology Data Exchange (ETDEWEB)

    Berg, Max; Bing, Dennis; Petrignani, Annemieke; Wolf, Andreas [Max-Planck-Institut fuer Kernphysik, Heidelberg (Germany)

    2010-07-01

    The triatomic hydrogen ion H{sub 3}{sup +} is a highly reactive key component in many astrophysical and technological plasmas. Being the simplest polyatomic molecule, it is also an important benchmark system against which various quantum mechanical calculations are tested. While the rovibrational levels near the triangular equilibrium structure are well understood, the rovibrational spectrum of this elementary system at strongly deformed geometry, above the barrier to linearity near 10000 cm{sup -1}, represents a formidable task for theory. Its experimental exploration so far ended slightly above 13900 cm{sup -1} from the ground state E{sub 0}({lambda}{proportional_to}720 nm). We report new measurements in a cryogenic 22 pole trap in the range of very high vibrational overtones, reaching levels up to {proportional_to}16500 cm{sup -1} ({lambda}{proportional_to}600 nm) from E{sub 0}. Chemical probing spectroscopy revealed its use for ultra-sensitive detection of transitions six to seven orders of magnitude weaker than the fundamental. Aside from the transition frequencies ({+-}0.005 cm{sup -1}), we present results from a new method to derive precise transition intensities, helping theoretical assignment of the lines.

  5. Quantitative Surface Chirality Detection with Sum Frequency Generation Vibrational Spectroscopy: Twin Polarization Angle Approach

    International Nuclear Information System (INIS)

    Wei, Feng; Xu, Yanyan; Guo, Yuan; Liu, Shi-lin; Wang, Hongfei

    2009-01-01

    Here we report a novel twin polarization angle (TPA) approach in the quantitative chirality detection with the surface sum-frequency generation vibrational spectroscopy (SFG-VS). Generally, the achiral contribution dominates the surface SFG-VS signal, and the pure chiral signal is usually two or three orders of magnitude smaller. Therefore, it has been difficult to make quantitative detection and analysis of the chiral contributions to the surface SFG-VS signal. In the TPA method, by varying together the polarization angles of the incoming visible light and the sum frequency signal at fixed s or p polarization of the incoming infrared beam, the polarization dependent SFG signal can give not only direct signature of the chiral contribution in the total SFG-VS signal, but also the accurate measurement of the chiral and achiral components in the surface SFG signal. The general description of the TPA method is presented and the experiment test of the TPA approach is also presented for the SFG-VS from the S- and R-limonene chiral liquid surfaces. The most accurate degree of chiral excess values thus obtained for the 2878 cm -1 spectral peak of the S- and R-limonene liquid surfaces are (23.7±0.4)% and (25.4±1.3)%, respectively.

  6. Structural characterization of CO-inhibited Mo-nitrogenase by combined application of nuclear resonance vibrational spectroscopy, extended X-ray absorption fine structure, and density functional theory: new insights into the effects of CO binding and the role of the interstitial atom.

    Science.gov (United States)

    Scott, Aubrey D; Pelmenschikov, Vladimir; Guo, Yisong; Yan, Lifen; Wang, Hongxin; George, Simon J; Dapper, Christie H; Newton, William E; Yoda, Yoshitaka; Tanaka, Yoshihito; Cramer, Stephen P

    2014-11-12

    The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm(-1) mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N2ase variant. In the frequency region above 450 cm(-1), additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by (13)CO isotope shifts). The EXAFS for wild-type N2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal -CO and a partially reduced -CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational "shake" modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N2 reactivity of N2ase are discussed.

  7. Vibration-based Energy Harvesting Systems Characterization Using Automated Electronic Equipment

    Directory of Open Access Journals (Sweden)

    Ioannis KOSMADAKIS

    2015-04-01

    Full Text Available A measurement bench has been developed to fully automate the procedure for the characterization of a vibration-based energy scavenging system. The measurement system is capable of monitoring all important characteristics of a vibration harvesting system (input and output voltage, current, and other parameters, frequency and acceleration values, etc.. It is composed of a PC, typical digital measuring instruments (oscilloscope, waveform generator, etc., certain sensors and actuators, along with a microcontroller based automation module. The automation of the procedure and the manipulation of the acquired data are performed by LabVIEW software. Typical measurements of a system consisting of a vibrating source, a vibration transducer and an active rectifier are presented.

  8. Infrared and Raman Vibrational Spectroscopies Reveal the Palette of Frescos Found in the Medieval Monastery of Karaach Teke

    International Nuclear Information System (INIS)

    Zorba, T.; Paraskevopoulos, K.M.; Pavlidou, E.; Andrikopoulos, K.S.; Daniilia, S.; Popkonstantinov, K.; Kostova, R.; Platnyov, V.

    2007-01-01

    Vibrational spectroscopy is applied on samples obtained from the excavation area of the medieval Monastery (10 th century) of Karaach-Teke in Bulgaria. The results of the corresponding study, reveal the type of materials used for the creation of the wall-paintings and give evidence of Byzantine influence, a fact that further supports the well known impact of Byzantium on the technology and thematic-aesthetic features of iconography in Bulgaria during this era. In addition, the complementarity of FTIR and -Raman spectroscopies in the identification of pigments is indicated

  9. Trimethylamine-N-oxide: its hydration structure, surface activity, and biological function, viewed by vibrational spectroscopy and molecular dynamics simulations.

    Science.gov (United States)

    Ohto, Tatsuhiko; Hunger, Johannes; Backus, Ellen H G; Mizukami, Wataru; Bonn, Mischa; Nagata, Yuki

    2017-03-08

    The osmolyte molecule trimethylamine-N-oxide (TMAO) stabilizes the structure of proteins. As functional proteins are generally found in aqueous solutions, an important aspect of this stabilization is the interaction of TMAO with water. Here, we review, using vibrational spectroscopy and molecular dynamics simulations, recent studies on the structure and dynamics of TMAO with its surrounding water molecules. This article ends with an outlook on the open questions on TMAO-protein and TMAO-urea interactions in aqueous environments.

  10. Study of calcification formation and disease diagnostics utilising advanced vibrational spectroscopy

    Science.gov (United States)

    Kerssens, Marleen Maartje

    The accurate and safe diagnosis of breast cancer is a significant societal issue, with annual disease incidence of 48,000 women and around 370 men in the UK. Early diagnosis of the disease allows more conservative treatments and better patient outcomes. Microcalcifications in breast tissue are an important indicator for breast cancers, and often the only sign of their presence. Several studies have suggested that the type of calcification formed may act as a marker for malignancy and its presence may be of biological significance. In this work, breast calcifications are studied with FTIR, synchrotron FTIR, ATR FTIR, and Raman mapping to explore their disease specific composition. From a comparison between vibrational spectroscopy and routine staining procedures it becomes clear that calcium builds up prior to calcification formation. Raman and FTIR indicate the same size for calcifications and are in agreement with routine staining techniques. From the synchrotron FTIR measurements it can be proven that amide is present in the centre of the calcifications and the intensity of the bands depends on the pathology. Special attention is paid to the type of carbonate substitution in the calcifications relating to different pathology grades. In contrast to mammography, Raman spectroscopy has the capability to distinguish calcifications based on their chemical composition. The ultimate goal is to turn the acquired knowledge from the mapping studies into a clinical tool based on deep Raman spectroscopy. Deep Raman techniques have a considerable potential to reduce large numbers of normal biopsies, reduce the time delay between screening and diagnosis and therefore diminish patient anxiety. In order to achieve this, a deep Raman system is designed and after evaluation of its performance tested on buried calcification standards in porcine soft tissue and human mammary tissue. It is shown that, when the calcification is probed through tissue, the strong 960 cm-1 phosphate band

  11. Synchrotron radiation-induced contamination on LiF window: Characterization by Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, P. K., E-mail: praveenyadav@rrcat.gov.in [Material Research Laboratory, Indus Synchrotron Utilization Division (India); Swami, M. K. [Laser Biomedical Applications & Instrumentation Division, Raja Ramanna Centre for Advanced Technology, Indore-452013 (India)

    2016-05-23

    Characterization of synchrotron induced contamination on optical elements and their cleaning are serious issues in beam lines. We used Raman spectroscopy for characterization of synchrotron induced contamination layer on LiF window (used in high resolution vacuum ultra violet beam line). Three peaks at 1035 cm{sup −1} (corresponding to C-C sp{sup 3} vibrations), 1563 cm{sup −1} and 1375 cm{sup −1} (corresponding to G and D bands of carbon) are observed. By data fitting I(D)/I(G) ratio (0.84) and FWHM(G)=124 cm{sup −1} was obtained. Comparison with available literature indicates that the carbon might be present in the form of rings of hydrogenated amorphous carbon a-C:H (GLHC) with atomic hydrogen concentration about 15% with both sp{sup 2} and sp{sup 3} hybridization.

  12. Characterizing Sources of Small DC Motor Noise and Vibration

    Directory of Open Access Journals (Sweden)

    Yong Thung Cho

    2018-02-01

    Full Text Available Small direct current (DC motors are widely used due to their low cost and compact structure. Small DC motors of various designs are available on the market in different sizes. The smaller the motor, the more closely it may be used by individuals. Contrary to the size and simplicity of these motors in terms of structural design, sources of motor noise and vibration can be quite diverse and complicated. In this study, the source of motor noise and vibration was visualized over a very wide range of frequencies. The particle velocity of the motor was reconstructed from nearfield sound pressure measurements of motor noise. In addition to noncontact measurements conducted on a motor running at constant speed, the particle velocity of a stationary motor due to the impulse of an impact hammer was measured with an accelerometer. Furthermore, motor noise was measured under motor run-up conditions with different rotational speeds. As a result, by combination of these three methods, the sources of motor noise were accurately identified over a wide range of frequencies.

  13. Interpenetrating polymer network membranes for fuel cells: infrared vibrational spectroscopy; Membranes baseadas dm redes polimericas interpenetrantes para celulas a combustivel: estudo por espectroscopia vibracional no infravermelho

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Felipe A.M.; Rocco, Ana Maria [Grupo de Materiais Condutores e Energia, Escola de Quimica, Universidade Federal do Rio de Janeiro, RJ (Brazil)], e-mail: amrocco@eq.ufrj.br; Pereira, Robson Pacheco [Instituto de Ciencias Exatas, Universidade Federal Fluminense (UFF), Volta Redonda, RJ (Brazil)

    2011-07-01

    In the present work, proton conductive membranes based on IPN matrices doped with H{sub 3}PO{sub 4} were developed. The characterization by infrared vibrational spectroscopy evidenced the polymerization of DGEBA and the immobilization of PEI chains, originating a structure containing basic sites suitable for proton coordination and conduction. The FTIR characterization evidenced the polymerization of DGEBA in the presence of PEI thus forming Semi-IPN membranes which, after doped with H{sub 3}PO{sub 4}, exhibited conductivity values of 10{sup -4} W{sup -1}cm{sup -1} at room temperature and 10{sup -3} {omega}{sup -1}cm{sup -1} at 80 degree C, as well as a dependency of conductivity with temperature following the Arrhenius model. The activation energy values (14,33 and 12,96 kJ.mol{sup -1}) indicated a proton conduction mechanism predominantly vehicular in the matrices studied under 100% relative humidity. (author)

  14. Intrinsic Chirality and Prochirality at Air/R-(+)- and S-(-)-Limonene Interfaces: Spectral Signatures with Interference Chiral Sum-Frequency Generation Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Li; Zhang, Yun; Wei, Zhehao; Wang, Hongfei

    2014-06-04

    We report in this work detailed measurements on the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050cm-1) of the air/liquid interfaces of R-limonene and S-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the equal amount (50/50) racemic mixture show that the enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit spectral signature from chiral response of the Cα-H stretching mode, and spectral signature from prochiral response of the CH2 asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-limonene to S-limonene, and disappears for the 50/50 racemic mixture. While the prochiral spectral feature of the CH2 asymmetric stretching mode is the same for R-limonene and S-limonene, and also surprisingly remains the same for the 50/50 racemic mixture. These results provided detail information in understanding the structure and chirality of molecular interfaces, and demonstrated the sensitivity and potential of SFG-VS as unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

  15. Effects of temperature and other experimental variables on single molecule vibrational spectroscopy with the scanning tunneling microscope

    International Nuclear Information System (INIS)

    Lauhon, L. J.; Ho, W.

    2001-01-01

    Inelastic electron tunneling spectroscopy (IETS) was performed on single molecules with a variable temperature scanning tunneling microscope. The peak intensity, width, position, and line shape of single molecule vibrational spectra were studied as a function of temperature, modulation bias, bias polarity, and tip position for the (C--H,C--D) stretching vibration of acetylene (C 2 H 2 ,C 2 D 2 ) on Cu(001). The temperature broadening of vibrational peaks was found to be a consequence of Fermi smearing as in macroscopic IETS. The modulation broadening of vibrational peaks assumed the expected form for IETS. Extrapolation of the peak width to zero temperature and modulation suggested an intrinsic width of ∼4 meV due primarily to instrumental broadening. The inelastic tunneling cross section at negative bias was reduced by a factor of 1.7 for the C--H stretch mode. Low energy modes of other molecules did not show such a reduction. There was no evidence of a tip-induced Stark shift in the peak positions. The spatial variation of the inelastic signal was measured to determine the junction stability necessary for the acquisition of single molecule vibrational spectra

  16. Molecular and vibrational structure of diphenylether and its 4,4' -dibromo derivative. Infrared linear dichroism spectroscopy and density functional theory calculations

    DEFF Research Database (Denmark)

    Eriksen, Troels K; Karlsen, Eva; Spanget-Larsen, Jens

    2015-01-01

    The title compounds were investigated by means of Linear Dichroism (LD) IR spectroscopy on samples partially aligned in uniaxially stretched low-density polyethylene and by density functional theory calculations. Satisfactory overall agreement between observed and calculated vibrational wavenumbers...

  17. Sum Frequency Generation Vibrational Spectroscopy and Kinetic Study of 2-Methylfuran and 2,5-Dimethylfuran Hydrogenation over 7 nm Platinum Cubic Nanoparticles

    KAUST Repository

    Aliaga, Cesar; Tsung, Chia-Kuang; Alayoglu, Selim; Komvopoulos, Kyriakos; Yang, Peidong; Somorjai, Gabor A.

    2011-01-01

    Sum frequency generation vibrational spectroscopy and kinetic measurements obtained from gas chromatography were used to study the adsorption and hydrogenation of 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) over cubic Pt nanoparticles of 7 nm

  18. Characterization of Hydrogen Bonds by IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vojta, D.

    2012-05-01

    Full Text Available In the identification and quantification of hydrogen bond, as one of the most abundant non-covalent interactions in phenomena like self-assembly and molecular recognition, IR spectrosopy has been employed as the most sensitive method. The performance of the high dilution method enables determination of the stability constant of hydrogen-bonded complex as one of the most important thermodynamic quantities used in their characterization. However, the alleged experimental simplicity of the mentioned method is loaded with errors originating not only from researcher intervention but also independent from it. The second source of error is particularly emphasized and elaborated in this paper, which is designed as the recipe for the successful characterization of hydrogen bonds. Besides the enumeration of all steps in the determination of hydrogen-bonded stability constants, the reader can be acquainted with the most important ex perimental conditions that should be fulfilled in order to minimize the naturally occurring errors in this type of investigation. In the spectral analysis, the application of both uni- and multivariate approach has been discussed. Some computer packages, considering the latter, are mentioned, described, and recommended. KUI -10/2012Received August 1, 2011Accepted October 24, 2011

  19. Characterization of Egyptian coal from Sinai using Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Eissa, N.A.; Abdel Meguid, M.M.; Deriu, A.; Albanese, G.

    1983-08-01

    The presence of iron bearing minerals in coal makes the Moessbauer Spectroscopy (MS) extremely useful for characterization of coals from different localities. In this paper the MS has been applied to characterize Egyptian coal from Sinai (Maghara). The chemical analysis of this coal is given. The MS results showed that pyritic sulphur (pyrite and marcasite) is the only bearing mineral in Egyptian coal. A review is given for the iron bearing minerals in coals from different countries measured by MS. (author)

  20. Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Christopher [Univ. of California, Berkeley, CA (United States)

    2014-05-15

    Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

  1. Characterization Of Cobalt-Exchanged Zeolite A By DRIFT Spectroscopy

    Science.gov (United States)

    Kappers, M. J.; van der Maas, John H.; Chalmers, J. M.; Howard, J.

    1989-12-01

    In-situ DRIFT spectroscopy has been succesfully used for the characterization of Co4Na4-A. Dehydration of the zeolite A appears to involve formation and breakdown of hydration complexes and hydrolysis. The position of cations and hydroxyl groups within the zeolite structure was derived from the adsorption of carbon monoxide and acetonitrile.

  2. Characterization of Vocal Fold Vibration in Sulcus Vocalis Using High-Speed Digital Imaging

    Science.gov (United States)

    Yamauchi, Akihito; Yokonishi, Hisayuki; Imagawa, Hiroshi; Sakakibara, Ken-Ichi; Nito, Takaharu; Tayama, Niro; Yamasoba, Tatsuya

    2017-01-01

    Purpose: The aim of the present study was to qualitatively and quantitatively characterize vocal fold vibrations in sulcus vocalis by high-speed digital imaging (HSDI) and to clarify the correlations between HSDI-derived parameters and traditional vocal parameters. Method: HSDI was performed in 20 vocally healthy subjects (8 men and 12 women) and…

  3. Vibrational and chiroptical spectroscopic characterization of gamma-turn model cyclic tetrapeptides containing two beta-Ala residues.

    Science.gov (United States)

    Vass, Elemér; Majer, Zsuzsa; Kohalmy, Krisztina; Hollósi, Miklós

    2010-08-01

    The optical spectroscopic characterization of gamma-turns in solution is uncertain and their distinction from beta-turns is often difficult. This work reports systematic ECD and vibrational circular dichroism (VCD) spectroscopic studies on gamma-turn model cyclic tetrapeptides cyclo(Ala-beta-Ala-Pro-beta-Ala) (1), cyclo(Pro-beta-Ala-Pro-beta-Ala) (2) and cyclo(Ala-beta-Ala-Ala-beta-Ala) (3). Conformational analysis performed at the 6-31G(d)/B3LYP level of theory using an adequate PCM solvent model predicted one predominant conformer for 1-3, featuring two inverse gamma-turns. The ECD spectra in ACN of 1 and 2 are characterized by a negative n-->pi* band near 230 nm and a positive pi-->pi* band below 200 nm with a long wavelength shoulder. The ECD spectra in TFE of 1-3 show similar spectra with blue-shifted bands. The VCD spectra in ACN-d(3) of 1 and 2 show a +/-/+/- amide I sign pattern resulting from four uncoupled vibrations in the case of 1 and a sequence of two positive couplets in the case of 2. A -/+/+/- amide I VCD pattern was measured for 3 in TFE-d(2). All three peptides give a positive couplet or couplet-like feature (+/-) in the amide II region. VCD spectroscopy, in agreement with theoretical calculations revealed that low frequency amide I vibrations (at approximately 1630 cm(-1) or below) are indicative of a C(7) H-bonded inverse gamma-turns with Pro in position 2, while gamma-turns encompassing Ala absorb at higher frequency (above 1645 cm(-1)). Copyright 2010 Wiley-Liss, Inc.

  4. Millimeterwave spectroscopy of active laser plasmas; the excited vibrational states of HCN

    International Nuclear Information System (INIS)

    De Lucia, F.C.; Helminger, P.A.

    1977-01-01

    Millimeter and submillimeter microwave techniques have been used for the spectroscopic study of an HCN laser plasma. Forty-seven rotational transitions in 12 excited vibrational states have been observed. Numerous rotational, vibrational, and perturbation parameters have been calculated from these data. A discussion of experimental techniques is included

  5. Non-invasive vibrational SFG spectroscopy reveals that bacterial adhesion can alter the conformation of grafted "brush" chains on SAM.

    Science.gov (United States)

    Bulard, Emilie; Guo, Ziang; Zheng, Wanquan; Dubost, Henri; Fontaine-Aupart, Marie-Pierre; Bellon-Fontaine, Marie-Noëlle; Herry, Jean-Marie; Briandet, Romain; Bourguignon, Bernard

    2011-04-19

    Understanding bacterial adhesion on a surface is a crucial step to design new materials with improved properties or to control biofilm formation and eradication. Sum Frequency Generation (SFG) vibrational spectroscopy has been employed to study in situ the conformational response of a self-assembled monolayer (SAM) of octadecanethiol (ODT) on a gold film to the adhesion of hydrophilic and hydrophobic ovococcoid model bacteria. The present work highlights vibrational SFG spectroscopy as a powerful and unique non-invasive biophysical technique to probe and control bacteria interaction with ordered surfaces. Indeed, the SFG vibrational spectral changes reveal different ODT SAM conformations in air and upon exposure to aqueous solution or bacterial adhesion. Furthermore, this effect depends on the bacterial cell surface properties. The SFG spectral modeling demonstrates that hydrophobic bacteria flatten the ODT SAM alkyl chain terminal part, whereas the hydrophilic ones raise this ODT SAM terminal part. Microorganism-induced alteration of grafted chains can thus affect the desired interfacial functionality, a result that should be considered for the design of new reactive materials. © 2011 American Chemical Society

  6. Semi-quantitative prediction of a multiple API solid dosage form with a combination of vibrational spectroscopy methods.

    Science.gov (United States)

    Hertrampf, A; Sousa, R M; Menezes, J C; Herdling, T

    2016-05-30

    Quality control (QC) in the pharmaceutical industry is a key activity in ensuring medicines have the required quality, safety and efficacy for their intended use. QC departments at pharmaceutical companies are responsible for all release testing of final products but also all incoming raw materials. Near-infrared spectroscopy (NIRS) and Raman spectroscopy are important techniques for fast and accurate identification and qualification of pharmaceutical samples. Tablets containing two different active pharmaceutical ingredients (API) [bisoprolol, hydrochlorothiazide] in different commercially available dosages were analysed using Raman- and NIR Spectroscopy. The goal was to define multivariate models based on each vibrational spectroscopy to discriminate between different dosages (identity) and predict their dosage (semi-quantitative). Furthermore the combination of spectroscopic techniques was investigated. Therefore, two different multiblock techniques based on PLS have been applied: multiblock PLS (MB-PLS) and sequential-orthogonalised PLS (SO-PLS). NIRS showed better results compared to Raman spectroscopy for both identification and quantitation. The multiblock techniques investigated showed that each spectroscopy contains information not present or captured with the other spectroscopic technique, thus demonstrating that there is a potential benefit in their combined use for both identification and quantitation purposes. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Toward yrast spectroscopy in soft vibrational nuclei. A microscopic theory of the large amplitude collective motion of soft nuclei

    International Nuclear Information System (INIS)

    Marumori, Toshio; Kuriyama, Atsushi; Sakata, Fumihiko

    1980-01-01

    In a formally parallel way with that exciting progress has been recently achieved in understanding the yrast spectra of the rotational nuclei in terms of the quasi-particle motion in the rotating frame, an attempt to understand the yrast spectra of the vibrational nuclei in terms of the quasi-particle motion is proposed. The essential idea is to introduce the quasi-particle motion in a generalized vibrating frame, which can be regarded as a rotating frame in the gauge space of 'physical' phonons where the number of the physical phonons plays the role of the angular momentum. On the basis of a simple fundamental principle called as the 'invariance principle of the Schroedinger equation', which leads us to the 'maximal decoupling' between the physical phonon and the intrinsic modes, it is shown that the vibrational frame as well as the physical-phonon-number operator represented by the quasi-particles can be self-consistently determined. A new scope toward the yrast spectroscopy of the vibrational nuclei in terms of the quasi-particle motion is discussed

  8. Characterizing human activity induced impulse and slip-pulse excitations through structural vibration

    Science.gov (United States)

    Pan, Shijia; Mirshekari, Mostafa; Fagert, Jonathon; Ramirez, Ceferino Gabriel; Chung, Albert Jin; Hu, Chih Chi; Shen, John Paul; Zhang, Pei; Noh, Hae Young

    2018-02-01

    Many human activities induce excitations on ambient structures with various objects, causing the structures to vibrate. Accurate vibration excitation source detection and characterization enable human activity information inference, hence allowing human activity monitoring for various smart building applications. By utilizing structural vibrations, we can achieve sparse and non-intrusive sensing, unlike pressure- and vision-based methods. Many approaches have been presented on vibration-based source characterization, and they often either focus on one excitation type or have limited performance due to the dispersion and attenuation effects of the structures. In this paper, we present our method to characterize two main types of excitations induced by human activities (impulse and slip-pulse) on multiple structures. By understanding the physical properties of waves and their propagation, the system can achieve accurate excitation tracking on different structures without large-scale labeled training data. Specifically, our algorithm takes properties of surface waves generated by impulse and of body waves generated by slip-pulse into account to handle the dispersion and attenuation effects when different types of excitations happen on various structures. We then evaluate the algorithm through multiple scenarios. Our method achieves up to a six times improvement in impulse localization accuracy and a three times improvement in slip-pulse trajectory length estimation compared to existing methods that do not take wave properties into account.

  9. LABORATORY CHARACTERIZATION AND ASTROPHYSICAL DETECTION OF VIBRATIONALLY EXCITED STATES OF ETHYL CYANIDE

    Energy Technology Data Exchange (ETDEWEB)

    Daly, A. M.; Bermudez, C.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Area de Quimica-Fisica, Laboratorios de Espectroscopia y Bioespectroscopia, Unidad Asociada del CSIC, Universidad de Valladolid, E-47005 Valladolid (Spain); Lopez, A.; Tercero, B.; Cernicharo, J. [Department of Astrophysics, CAB, INTA-CSIC, Crta Torrejon, E-28850 Torrejon de Ardoz, Madrid (Spain); Pearson, J. C. [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Padadena, CA 91109 (United States); Marcelino, N., E-mail: adammichael.daly@uva.es, E-mail: cbermu@qf.uva.es, E-mail: jlalonso@qf.uva.es, E-mail: lopezja@cab.inta-csic.es, E-mail: terceromb@cab.inta-csic.es, E-mail: jcernicharo@cab.inta-csic.es, E-mail: John.C.Pearson@jpl.nasa.gov, E-mail: nmarceli@nrao.edu [National Radio Astronomy Observatory, 520 Edgemont Road, Charlottesville, VA 22903 (United States)

    2013-05-01

    Ethyl cyanide, CH{sub 3}CH{sub 2}CN, is an important interstellar molecule with a very dense rotational-vibrational spectrum. On the basis of new laboratory data in the range of 17-605 GHz and ab initio calculations, two new vibrational states, {nu}{sub 12} and {nu}{sub 20}, have been detected in molecular clouds of Orion. Laboratory data consist of Stark spectroscopy (17-110 GHz) and frequency-modulated spectrometers (GEM laboratory in Valladolid: 17-170, 270-360 GHz; Toyama: 26-200 GHz; Emory: 200-240 GHz; Ohio State: 258-368 GHz; and JPL: 270-318, 395-605 GHz). More than 700 distinct lines of each species were measured in J up to 71 and in K{sub a} up to 25. The states were fitted with Watson's S-reduction Hamiltonian. The two new states have been identified in the interstellar medium toward the Orion Nebula (Orion KL). The ground state, the isotopologues of CH{sub 3}CH{sub 2}CN, and the vibrationally excited states have been fitted to obtain column densities and to derive vibrational temperatures. All together, ethyl cyanide is responsible for more than 2000 lines in the observed frequency range of 80-280 GHz.

  10. Selective detection of crystalline cellulose in plant cell walls with sum-frequency-generation (SFG) vibration spectroscopy.

    Science.gov (United States)

    Barnette, Anna L; Bradley, Laura C; Veres, Brandon D; Schreiner, Edward P; Park, Yong Bum; Park, Junyeong; Park, Sunkyu; Kim, Seong H

    2011-07-11

    The selective detection of crystalline cellulose in biomass was demonstrated with sum-frequency-generation (SFG) vibration spectroscopy. SFG is a second-order nonlinear optical response from a system where the optical centrosymmetry is broken. In secondary plant cell walls that contain mostly cellulose, hemicellulose, and lignin with varying concentrations, only certain vibration modes in the crystalline cellulose structure can meet the noninversion symmetry requirements. Thus, SFG can be used to detect and analyze crystalline cellulose selectively in lignocellulosic biomass without extraction of noncellulosic species from biomass or deconvolution of amorphous spectra. The selective detection of crystalline cellulose in lignocellulosic biomass is not readily achievable with other techniques such as XRD, solid-state NMR, IR, and Raman analyses. Therefore, the SFG analysis presents a unique opportunity to reveal the cellulose crystalline structure in lignocellulosic biomass.

  11. Ag clustering investigation in laser irradiated ion-exchanged glasses by optical and vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Trave, E., E-mail: enrico.trave@unive.it [Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venezia, Dorsoduro 2137, I-30123 Venezia (Italy); Cattaruzza, E.; Gonella, F.; Calvelli, P. [Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venezia, Dorsoduro 2137, I-30123 Venezia (Italy); Quaranta, A. [Department of Materials Engineering and Industrial Technologies, University of Trento, via Mesiano 77, I-38050 Povo (Italy); Rahman, A.; Mariotto, G. [Department of Computer Science, University of Verona, Strada le Grazie 15, 37134 Verona (Italy)

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer We modify the properties of Ag{sup +} exchanged glasses by thermal and laser treatment. Black-Right-Pointing-Pointer The induced microstructural changes are analyzed by optical and Raman spectroscopy. Black-Right-Pointing-Pointer Ag-based species in the glass show a peculiar PL activity in the UV-Vis range. Black-Right-Pointing-Pointer Raman and OA analysis allow for determining the Ag cluster size evolution. Black-Right-Pointing-Pointer Laser processing leads to different cluster formation and fragmentation mechanisms. - Abstract: Ion exchange process is widely used to dope silicate glass layers with silver for several applications, ranging from light waveguide to nanostructured composite glass fabrication. The silver-doped structure and its physical properties depend on the preparation parameters as well as on subsequent treatments. In particular, laser irradiation of the ion exchanged glasses has been demonstrated to be an effective tool to control cluster size and size distribution. Nevertheless, a complete comprehension of the basic phenomena and a systematic characterization of these systems are still lacking. In this paper, an extended optical characterization is presented for soda-lime glass slides, doped with silver by Ag{sup +}-Na{sup +} ion exchange, thermally treated and irradiated with a Nd:YAG laser beam at different wavelengths, and for different energy density. The samples were characterized by various spectroscopic techniques, namely, optical absorption, photoluminescence and micro-Raman analysis. The availability of all these characterization techniques allowed pointing out a suitable scenario for the Ag clustering evolution as a function of the ion exchange, annealing and laser irradiation parameters.

  12. Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

    Science.gov (United States)

    Wang, Hong-Fei

    2016-12-01

    Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

  13. Characterizing aging effects of lithium ion batteries by impedance spectroscopy

    International Nuclear Information System (INIS)

    Troeltzsch, Uwe; Kanoun, Olfa; Traenkler, Hans-Rolf

    2006-01-01

    Impedance spectroscopy is one of the most promising methods for characterizing aging effects of portable secondary batteries online because it provides information about different aging mechanisms. However, application of impedance spectroscopy 'in the field' has some higher requirements than for laboratory experiments. It requires a fast impedance measurement process, an accurate model applicable with several batteries and a robust method for model parameter estimation. In this paper, we present a method measuring impedance at different frequencies simultaneously. We propose to use a composite electrode model, capable to describe porous composite electrode materials. A hybrid method for parameter estimation based on a combination of evolution strategy and Levenberg-Marquardt method allowed a robust and fast parameter calculation. Based on this approach, an experimental investigation of aging effects of a lithium ion battery was carried out. After 230 discharge/charge cycles, the battery showed a 14% decreased capacity. Modeling results show that series resistance, charge transfer resistance and Warburg coefficient changed thereby their values by approximately 60%. A single frequency impedance measurement, usually carried out at 1 kHz, delivers only information about series resistance. Impedance spectroscopy allows additionally the estimation of charge transfer resistance and Warburg coefficient. This fact and the high sensitivity of model parameters to capacity change prove that impedance spectroscopy together with an accurate modeling deliver information that significantly improve characterization of aging effects

  14. Characterizing aging effects of lithium ion batteries by impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Troeltzsch, Uwe [University of the Bundeswehr Munich Institute for Measurement and Automation, 85579 Neubiberg (Germany)]. E-mail: uwe.troeltzsch@unibw-muenchen.de; Kanoun, Olfa [University of the Bundeswehr Munich Institute for Measurement and Automation, 85579 Neubiberg (Germany); Traenkler, Hans-Rolf [University of the Bundeswehr Munich Institute for Measurement and Automation, 85579 Neubiberg (Germany)

    2006-01-20

    Impedance spectroscopy is one of the most promising methods for characterizing aging effects of portable secondary batteries online because it provides information about different aging mechanisms. However, application of impedance spectroscopy 'in the field' has some higher requirements than for laboratory experiments. It requires a fast impedance measurement process, an accurate model applicable with several batteries and a robust method for model parameter estimation. In this paper, we present a method measuring impedance at different frequencies simultaneously. We propose to use a composite electrode model, capable to describe porous composite electrode materials. A hybrid method for parameter estimation based on a combination of evolution strategy and Levenberg-Marquardt method allowed a robust and fast parameter calculation. Based on this approach, an experimental investigation of aging effects of a lithium ion battery was carried out. After 230 discharge/charge cycles, the battery showed a 14% decreased capacity. Modeling results show that series resistance, charge transfer resistance and Warburg coefficient changed thereby their values by approximately 60%. A single frequency impedance measurement, usually carried out at 1 kHz, delivers only information about series resistance. Impedance spectroscopy allows additionally the estimation of charge transfer resistance and Warburg coefficient. This fact and the high sensitivity of model parameters to capacity change prove that impedance spectroscopy together with an accurate modeling deliver information that significantly improve characterization of aging effects.

  15. UV-VIS and photoluminescence spectroscopy for nanomaterials characterization

    CERN Document Server

    2013-01-01

    Second volume of a 40-volume series on nanoscience and nanotechnology, edited by the renowned scientist Challa S.S.R. Kumar. This handbook gives a comprehensive overview about UV-visible and photoluminescence spectroscopy for the characterization of nanomaterials. Modern applications and state-of-the-art techniques are covered and make this volume essential reading for research scientists in academia and industry in the related fields.

  16. Fabrication and vibration characterization of curcumin extracted from turmeric (Curcuma longa) rhizomes of the northern Vietnam.

    Science.gov (United States)

    Van Nong, Hoang; Hung, Le Xuan; Thang, Pham Nam; Chinh, Vu Duc; Vu, Le Van; Dung, Phan Tien; Van Trung, Tran; Nga, Pham Thu

    2016-01-01

    In this report, we present the research results on using the conventional method and microwave technology to extract curcuminoid from turmeric roots originated in different regions of Northern Vietnam. This method is simple, yet economical, non-toxic and still able to achieve high extraction performance to get curcuminoid from turmeric roots. The detailed results on the Raman vibration spectra combined with X-ray powder diffraction and high-performance liquid chromatography/mass spectrometry allowed the evaluation of each batch of curcumin crystalline powder sample received, under the conditions of applied fabrication technology. Also, the absorption and fluorescence spectroscopies of the samples are presented in the paper. The information to be presented in this paper: absorption and fluorescence spectroscopies of the samples; new experimental study results on applied technology to mass-produce curcumin from turmeric rhizomes; comparative study results between fabricated samples and marketing curcumin products-to state the complexity of co-existing crystalline phase in curcumin powder samples. We noticed that, it is possible to use the vibration line at ~959 cm(-1)-characteristic of the ν C=O vibration, and the ~1625 cm(-1) line-characteristic of the ν C=O and ν C=C vibration in curcumin molecules, for preliminary quality assessment of naturally originated curcumin crystalline powder samples. Data on these new optical spectra will contribute to the bringing of detailed information on natural curcumin in Vietnam, serving research purposes and applications of natural curcumin powder and nanocurcumin in Vietnam, as well as being initial materials for the pharmaceutical, cosmetics or functional food industries.

  17. Vibrational spectroscopy of SnBr4 and CCl4 using Lie algebraic ...

    Indian Academy of Sciences (India)

    experimentalists because of the development of new laser spectroscopic techniques. Wulfman played a ... used Lie algebraic methods to study the spectra of molecules (vibron model) using. U(4) algebra. ..... to vibrations of gas molecules.

  18. Effects of cations and cholesterol with sphingomyelin membranes investigated by high-resolution broadband sum frequency vibrational spectroscopy

    Science.gov (United States)

    Zhang, Zhen; Feng, Rong-juan; Li, Yi-yi; Liu, Ming-hua; Guo, Yuan

    2017-08-01

    Sphingomyelin(SM) is specifically enriched in the plasma membrane of mammalian cells. Its molecular structure is compose by N-acyl-Derythro-sphingosylphosphorylcholine. The function of the SM related to membrane signaling and protein trafficking are relied on the interactions of the SM, cations, cholesterol and proteins. In this report, the interaction of three different nature SMs, cations and cholesterol at air/aqueous interfaces studied by high-resolution broadband sum frequency vibrational spectroscopy, respectively. Our results shed lights on understanding the relationship between SMs monolayer, cholesterol and Cations.

  19. Femtosecond stimulated Raman spectroscopy as a tool to detect molecular vibrations in ground and excited electronic states

    Energy Technology Data Exchange (ETDEWEB)

    Gelin, Maxim F.; Domcke, Wolfgang [Department of Chemistry, Technische Universität München, D-85747 Garching (Germany); Rao, B. Jayachander [Departamento de Química and Centro de Química, Universidade de Coimbra, 3004-535 Coimbra (Portugal)

    2016-05-14

    We give a detailed theoretical analysis of the simplest variant of femtosecond stimulated Raman spectroscopy, where a picosecond Raman pump pulse and a femtosecond Raman probe pulse are applied resonantly to a chromophore in thermal equilibrium in the ground electronic state. We demonstrate that this technique is capable of the detection of dephasing-free Raman-like lines revealing vibrational modes not only in the electronic ground state but also in the excited electronic state of the chromophore. The analytical results obtained with simplifying assumptions for the shape of the laser pulses are substantiated by numerical simulations with realistic laser pulses, employing the equation-of-motion phase-matching approach.

  20. Nuclear resonance vibrational spectroscopy applied to [Fe(OEP)(NO)]: the vibrational assignments of five-coordinate ferrous heme-nitrosyls and implications for electronic structure.

    Science.gov (United States)

    Lehnert, Nicolai; Galinato, Mary Grace I; Paulat, Florian; Richter-Addo, George B; Sturhahn, Wolfgang; Xu, Nan; Zhao, Jiyong

    2010-05-03

    This study presents Nuclear Resonance Vibrational Spectroscopy (NRVS) data on the five-coordinate (5C) ferrous heme-nitrosyl complex [Fe(OEP)(NO)] (1, OEP(2-) = octaethylporphyrinato dianion) and the corresponding (15)N(18)O labeled complex. The obtained spectra identify two isotope sensitive features at 522 and 388 cm(-1), which shift to 508 and 381 cm(-1), respectively, upon isotope labeling. These features are assigned to the Fe-NO stretch nu(Fe-NO) and the in-plane Fe-N-O bending mode delta(ip)(Fe-N-O), the latter has been unambiguously assigned for the first time for 1. The obtained NRVS data were simulated using our quantum chemistry centered normal coordinate analysis (QCC-NCA). Since complex 1 can potentially exist in 12 different conformations involving the FeNO and peripheral ethyl orientations, extended density functional theory (DFT) calculations and QCC-NCA simulations were performed to determine how these conformations affect the NRVS properties of [Fe(OEP)NO]. These results show that the properties and force constants of the FeNO unit are hardly affected by the conformational changes involving the ethyl substituents. On the other hand, the NRVS-active porphyrin-based vibrations around 340-360, 300-320, and 250-270 cm(-1) are sensitive to the conformational changes. The spectroscopic changes observed in these regions are due to selective mechanical couplings of one component of E(u)-type (in ideal D(4h) symmetry) porphyrin-based vibrations with the in-plane Fe-N-O bending mode. This leads to the observed variations in Fe(OEP) core mode energies and NRVS intensities without affecting the properties of the FeNO unit. The QCC-NCA simulated NRVS spectra of 1 show excellent agreement with experiment, and indicate that conformer F is likely present in the samples of this complex investigated here. The observed porphyrin-based vibrations in the NRVS spectra of 1 are also assigned based on the QCC-NCA results. The obtained force constants of the Fe-NO and N

  1. Characterization of Crystal Chirality in Amino Acids Using Low-Frequency Raman Spectroscopy.

    Science.gov (United States)

    Aviv, Hagit; Nemtsov, Irena; Mastai, Yitzhak; Tischler, Yaakov R

    2017-10-19

    We present a new method for differentiating racemic crystals from enantiopure crystals. Recently, developments in optical filters have enabled the facile use of Raman spectroscopy to detect low-frequency vibrational (LFV) modes. Here, for the first time, we use Raman spectroscopy to characterize the LFV modes for crystalline organic materials composed of chiral molecules. The LF-Raman spectra of racemic and enantiopure crystals exhibit a significant variation, which we attribute to different hydrogen-bond networks in the chiral crystal structures. Across a representative set of amino acids, we observed that when comparing racemic versus enantiopure crystals, the available LFV modes and their relative scattering intensity are strong functions of side chain polarity. Thus, LF-Raman can be used as a method that is complementary to the currently used methods for characterizing crystal chirality due to simpler, faster, and more sensitive measurements, along with the small sample size required, which is limited by the laser-beam diameter in the focus.

  2. a Study of Vibrational Mode Coupling in 2-FLUOROETHANOL and 1,2-DIFLUOROETHANE Using High-Resolution Infrared Spectroscopy.

    Science.gov (United States)

    Mork, Steven Wayne

    High resolution infrared spectroscopy was used to examine intramolecular vibrational interactions in 2 -fluoroethanol (2FE) and 1,2-difluoroethane (DFE). A high resolution infrared spectrophotometer capable of better than 10 MHz spectral resolution was designed and constructed. The excitation source consists of three lasers: an argon-ion pumped dye laser which pumps a color -center laser. The infrared beam from the color-center laser is used to excite sample molecules which are rotationally and vibrationally cooled in a supersonic molecular beam. Rovibrational excitation of the sample molecules is detected by monitoring the kinetic energy of the molecular beam with a bolometer. The high resolution infrared spectrum of 2FE was collected and analyzed over the 2977-2990 cm^ {-1}^ectral region. This region contains the asymmetric CH stretch on the fluorinated carbon. The spectrum revealed extensive perturbations in the rotational fine structure. Analysis of these perturbations has provided a quantitative measure of selective vibrational mode coupling between the C-H stretch and its many neighboring dark vibrational modes. Interestingly, excitation of the C-H stretch is known to induce a photoisomerization reaction between 2FE's Gg^' and Tt conformers. Implications of the role of mode coupling in the reaction mechanism are also addressed. Similarly, the high resolution infrared spectrum of DFE was collected and analyzed over the 2978-2996 cm ^{-1}^ectral region. This region contains the symmetric combination of asymmetric C-H stretches in DFE. Perturbations in the rotational fine structure indicate vibrational mode coupling to a single dark vibrational state. The dark state is split by approximately 19 cm^{-1} due to tunneling between two identical gauche conformers. The coupling mechanism is largely anharmonic with a minor component of B/C-plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. The coupled vibrational

  3. Raman spectroscopy for the microbiological characterization and identification of medically relevant bacteria

    Science.gov (United States)

    Hamasha, Khozima Mahmoud

    The detection and identification of pathogenic bacteria has become more important than ever due to the increase of potential bioterrorism threats and the high mortality rate of bacterial infections worldwide. Raman spectroscopy has recently gained popularity as an attractive robust approach for the molecular characterization, rapid identification, and accurate classification of a wide range of bacteria. In this dissertation, Raman spectroscopy utilizing advanced statistical techniques was used to identify and discriminate between different pathogenic and non-pathogenic bacterial strains of E. coli and Staphylococcus aureus bacterial species by probing the molecular compositions of the cells. The five-carbon sugar xylitol, which cannot be metabolized by the oral and nasopharyngeal bacteria, had been recognized by clinicians as a preventive agents for dental caries and many studies have demonstrated that xylitol causes a reduction in otitis media (chronic inner ear infections) and other nasopharyngeal infections. Raman spectroscopy was used to characterize the uptake and metabolic activity of xylitol in pathogenic (viridans group Streptococcus) and nonpathogenic (E. coli) bacteria by taking their Raman spectra before xylitol exposure and after growing with xylitol and quantifying the significant differences in the molecular vibrational modes due to this exposure. The results of this study showed significant stable spectral changes in the S. viridians bacteria induced by xylitol and those changes were not the same as in some E. coli strains. Finally, Raman spectroscopy experiments were conducted to provide important information about the function of a certain protein (wag31) of Mycobacterium tuberculosis using a relative non-pathogenic bacterium called Mycobacterium smegmatis. Raman spectra of conditional mutants of bacteria expressing three different phosphorylation forms of wag31 were collected and analyzed. The results show that that the phosphorylation of wag31

  4. Use of photoacoustic mid-infrared spectroscopy to characterize soil properties and soil organic matter stability

    Science.gov (United States)

    Peltre, Clement; Bruun, Sander; Du, Changwen; Stoumann Jensen, Lars

    2014-05-01

    The persistence of soil organic matter (SOM) is recognized as a major ecosystem property due to its key role in earth carbon cycling, soil quality and ecosystem services. SOM stability is typically studied using biological methods such as measuring CO2-C evolution from microbial decomposition of SOM during laboratory incubation or by physical or chemical fractionation methods, allowing the separation of a labile fraction of SOM. However these methods are time consuming and there is still a need for developing reliable techniques to characterize SOM stability, providing both quantitative measurements and qualitative information, in order to improve our understanding of the mechanisms controlling SOM persistence. Several spectroscopic techniques have been used to characterize and predict SOM stability, such as near infrared reflectance spectroscopy (NIRS) and diffuse reflectance mid-infrared spectroscopy (DRIFT). The latter allows a proper identification of spectral regions corresponding to vibrations of specific molecular or functional groups associated with SOM lability. However, reflectance spectroscopy for soil analyses raises some difficulties related to the low reflectance of soils, and to the high influence of particle size. In the last three decades, the progresses in microphone sensitivity dramatically increased the performance of photoacoustic Fourier transform mid-infrared spectroscopy (FTIR-PAS). This technique offers benefits over reflectance spectroscopy techniques, because particle size and the level of sample reflectance have little effect of on the PAS signal, since FTIR-PAS is a direct absorption technique. Despite its high potential for soil analysis, only a limited number of studies have so far applied FTIR-PAS for soil characterization and its potential for determining SOM degradability still needs to be investigated. The objective of this study was to assess the potential of FTIR-PAS for the characterization of SOM decomposability during

  5. Strain characterization of FinFETs using Raman spectroscopy

    International Nuclear Information System (INIS)

    Kaleli, B.; Hemert, T. van; Hueting, R.J.E.; Wolters, R.A.M.

    2013-01-01

    Metal induced strain in the channel region of silicon (Si) fin-field effect transistor (FinFET) devices has been characterized using Raman spectroscopy. The strain originates from the difference in thermal expansion coefficient of Si and titanium-nitride. The Raman map of the device region is used to determine strain in the channel after preparing the device with the focused ion beam milling. Using the Raman peak shift relative to that of relaxed Si, compressive strain values up to – 0.88% have been obtained for a 5 nm wide silicon fin. The strain is found to increase with reducing fin width though it scales less than previously reported results from holographic interferometry. In addition, finite-element method (FEM) simulations have been utilized to analyze the amount of strain generated after thermal processing. It is shown that obtained FEM simulated strain values are in good agreement with the calculated strain values obtained from Raman spectroscopy. - Highlights: ► Strain is characterized in nanoscale devices with Raman spectroscopy. ► There is a fin width dependence of the originated strain. ► Strain levels obtained from this technique is in correlation with device simulations

  6. Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy

    International Nuclear Information System (INIS)

    Maekawa, Hiroaki; Sul, Soohwan; Ge, Nien-Hui

    2013-01-01

    Highlights: ► Vibrational dynamics of conjugated C=O and N=N modes of ethyl diazoacetate was studied. ► Their frequency–frequency correlation functions are different. ► The dual-frequency 2D IR spectrum indicates anticorrelated frequency fluctuations. ► Correlation effects on dual-frequency 2D IR spectra are discussed. ► The existence of cis and trans conformers is revealed in 2D IR spectra. - Abstract: We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester C=O and diazo N=N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency–frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single C=O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anticorrelated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed

  7. Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Maekawa, Hiroaki; Sul, Soohwan [Department of Chemistry, University of California at Irvine, Irvine, CA 92697-2025 (United States); Ge, Nien-Hui, E-mail: nhge@uci.edu [Department of Chemistry, University of California at Irvine, Irvine, CA 92697-2025 (United States)

    2013-08-30

    Highlights: ► Vibrational dynamics of conjugated C=O and N=N modes of ethyl diazoacetate was studied. ► Their frequency–frequency correlation functions are different. ► The dual-frequency 2D IR spectrum indicates anticorrelated frequency fluctuations. ► Correlation effects on dual-frequency 2D IR spectra are discussed. ► The existence of cis and trans conformers is revealed in 2D IR spectra. - Abstract: We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester C=O and diazo N=N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency–frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single C=O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anticorrelated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed.

  8. Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)

    Science.gov (United States)

    Velarde, Luis; Wang, Hong-fei

    2013-08-01

    While in principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system, the inhomogeneous character of surface vibrations in sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with time-domain SFG-VS by mapping the decay of the vibrational polarization using ultrafast lasers, this due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough lineshape. Here, with the recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) technique, we show that the inhomogeneous lineshape can be obtained in the frequency-domain for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuir monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 ± 0.01 cm-1 with a total linewidth of 10.9 ± 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4.7 ± 0.4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8.1 ± 0.2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57° ± 2° from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accommodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.

  9. Final Technical Report: Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets

    Energy Technology Data Exchange (ETDEWEB)

    Douberly, Gary Elliott [Univ. of Georgia, Athens, GA (United States)

    2017-11-16

    The objective of our experimental research program is to isolate and stabilize transient intermediates and products of prototype combustion reactions. This will be accomplished by Helium Nanodroplet Isolation, a novel technique where liquid helium droplets freeze out high energy metastable configurations of a reacting system, permitting infrared spectroscopic characterizations of products and intermediates that result from hydrocarbon radical reactions with molecular oxygen and other small molecules relevant to combustion environments. The low temperature (0.4 K) and rapid cooling associated with He droplets provides a perfectly suited medium to isolate and probe a broad range of molecular radical and carbene systems important to combustion chemistry. The sequential addition of molecular species to He droplets often leads to the stabilization of high-energy, metastable cluster configurations that represent regions of the potential energy surface far from the global minimum. Single and double resonance IR laser spectroscopy techniques, along with Stark and Zeeman capabilities, are being used to probe the structural and dynamical properties of these systems.

  10. Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

    Science.gov (United States)

    Fu, Li; Zhang, Yun; Wei, Zhe-Hao; Wang, Hong-Fei

    2014-09-01

    We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface. © 2014 Wiley Periodicals, Inc.

  11. Overtone spectroscopy of the hydroxyl stretch vibration in hydroxylamine (NH2OH)

    International Nuclear Information System (INIS)

    Scott, J.L.; Luckhaus, D.; Brown, S.S.; Crim, F.F.

    1995-01-01

    We present photoacoustic spectra of the second (3ν OH ), third (4ν OH ), and fourth (5ν OH ) overtone bands of the hydroxyl stretch vibration in hydroxylamine. Asymmetric rotor simulations of the rovibrational contours provide rotational constants and an estimate of the homogeneous linewidth. The fourth overtone band appears anomalously broad relative to the two lower bands, reflecting a sharp increase in the rate of intramolecular vibrational energy redistribution (IVR). By contrast, the calculated density of states increases smoothly with energy. The homogeneous linewidth of the fourth overtone transition is similar to that measured by Luo et al. [J. Chem. Phys. 93, 9194 (1990)] for the predissociative sixth overtone band, supporting the conclusion that the broadening arises from increased (ro)vibrational coupling at an energy between the third and fourth overtone states

  12. Sum Frequency Generation Vibrational Spectroscopy of Adsorbed Amino Acids, Peptides and Proteins of Hydrophilic and Hydrophobic Solid-Water Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Holinga IV, George Joseph [Univ. of California, Berkeley, CA (United States)

    2010-09-01

    Sum frequency generation (SFG) vibrational spectroscopy was used to investigate the interfacial properties of several amino acids, peptides, and proteins adsorbed at the hydrophilic polystyrene solid-liquid and the hydrophobic silica solid-liquid interfaces. The influence of experimental geometry on the sensitivity and resolution of the SFG vibrational spectroscopy technique was investigated both theoretically and experimentally. SFG was implemented to investigate the adsorption and organization of eight individual amino acids at model hydrophilic and hydrophobic surfaces under physiological conditions. Biointerface studies were conducted using a combination of SFG and quartz crystal microbalance (QCM) comparing the interfacial structure and concentration of two amino acids and their corresponding homopeptides at two model liquid-solid interfaces as a function of their concentration in aqueous solutions. The influence of temperature, concentration, equilibration time, and electrical bias on the extent of adsorption and interfacial structure of biomolecules were explored at the liquid-solid interface via QCM and SFG. QCM was utilized to quantify the biological activity of heparin functionalized surfaces. A novel optical parametric amplifier was developed and utilized in SFG experiments to investigate the secondary structure of an adsorbed model peptide at the solid-liquid interface.

  13. Vibrational sum-frequency generation spectroscopy of lipid bilayers at repetition rates up to 100 kHz

    Science.gov (United States)

    Yesudas, Freeda; Mero, Mark; Kneipp, Janina; Heiner, Zsuzsanna

    2018-03-01

    Broadband vibrational sum-frequency generation (BB-VSFG) spectroscopy has become a well-established surface analytical tool capable of identifying the orientation and structure of molecular layers. A straightforward way to boost the sensitivity of the technique could be to increase the laser repetition rate beyond that of standard BB-VSFG spectrometers, which rely on Ti:sapphire lasers operating at repetition rates of 1-5 kHz. Nevertheless, possible thermally induced artifacts in the vibrational spectra due to higher laser average powers are unexplored. Here, we discuss laser power induced temperature accumulation effects that distort the BB-VSFG spectra of 1,2-diacyl-sn-glycero-3-phosphocholine at an interface between two transparent phases at repetition rates of 5, 10, 50, and 100 kHz at constant pulse energy. No heat-induced distortions were found in the spectra, suggesting that the increase in the laser repetition rate provides a feasible route to an improved signal-to-noise ratio or shorter data acquisition times in BB-VSFG spectroscopy for thin films on transparent substrates. The results have implications for future BB-VSFG spectrometers pushing the detection limit for molecular layers with low surface coverage.

  14. The photodissociation and reaction dynamics of vibrationally excited molecules

    Energy Technology Data Exchange (ETDEWEB)

    Crim, F.F. [Univ. of Wisconsin, Madison (United States)

    1993-12-01

    This research determines the nature of highly vibrationally excited molecules, their unimolecular reactions, and their photodissociation dynamics. The goal is to characterize vibrationally excited molecules and to exploit that understanding to discover and control their chemical pathways. Most recently the author has used a combination of vibrational overtone excitation and laser induced fluorescence both to characterize vibrationally excited molecules and to study their photodissociation dynamics. The author has also begun laser induced grating spectroscopy experiments designed to obtain the electronic absorption spectra of highly vibrationally excited molecules.

  15. Vibration-rotation spectrum of BH X1Σ+ by Fourier transform emission spectroscopy

    Science.gov (United States)

    Pianalto, F. S.; O'Brien, L. C.; Keller, P. C.; Bernath, P. F.

    1988-06-01

    The vibration-rotation emission spectrum of the BH X1Σ+ state was observed with the McMath Fourier transform spectrometer at Kitt Peak. The 1-0, 2-1, and 3-2 bands were observed in a microwave discharge of B2H6 in He. Spectroscopic constants of the individual vibrational levels and equilibrium molecular constants were determined. An RKR potential curve was calculated from the equilibrium constants. Alfred P. Sloan Fellow; Camille and Henry Dreyfus Teacher-Scholar.

  16. Vibrational spectroscopy of shock-compressed fluid N2 and O2

    International Nuclear Information System (INIS)

    Schmidt, S.C.; Moore, D.S.; Shaw, M.S.; Johnson, J.D.

    1987-01-01

    Single-pulse multiplex coherent anti-Stokes Raman scattering (CARS) was used to observe the vibrational spectra of liquid N 2 shock-compressed to several pressures and temperatures up to 41 GPa and 5200 K and liquid O 2 shock-compressed to several pressures and temperatures up to 10 GPa and 1000 K. For N 2 , the experimental spectra were compared to synthetic spectra calculated using a semiclassical model for CARS intensities and estimated vibrational frequencies, peak Raman susceptibilities, and Raman line widths. The question of excited state populations in the shock-compressed state is addressed

  17. Orientations of nonlocal vibrational modes from combined experimental and theoretical sum frequency spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Chase, Hilary M.; Chen, Shunli; Fu, Li; Upshur, Mary Alice; Rudshteyn, Benjamin; Thomson, Regan J.; Wang, Hong-Fei; Batista, Victor S.; Geiger, Franz M.

    2017-09-01

    Inferring molecular orientations from vibrational sum frequency generation (SFG) spectra is challenging in polarization combinations that result in low signal intensities, or when the local point group symmetry approximation fails. While combining experiments with density functional theory (DFT) could overcome this problem, the scope of the combined method has yet to be established. Here, we assess its feasibility of determining the distributions of molecular orientations for one monobasic ester, two epoxides and three alcohols at the vapor/fused silica interface. We find that molecular orientations of nonlocal vibrational modes cannot be determined using polarization-resolved SFG measurements alone.

  18. Analysis of functional organic molecules at noble metal surfaces by means of vibrational spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Leyssner, Felix

    2011-10-24

    The goal of this work is to optimize the efficiency of photoinduced molecular switching processes on surfaces via controlled variations of the adsorption and electronic properties of the switch. We investigated the influence of external stimuli, i.e. photons and thermal activation, on surface bound molecular switches undergoing trans/cis-isomerizations and ring-opening/closing-reactions, respectively. High resolution electron energy loss spectroscopy (HREELS) and sum-frequency generation (SFG) spectroscopy have been used as the main tools to investigate the adsorption behavior and the molecular switching properties. Two basic concepts of coupling the molecular switch to the surface have been studied: (i) physisorbed or weakly chemisorbed systems deposited on noble metal surfaces under UHV conditions and (ii) molecular switches bound covalently via anchor groups. In the HREELS study following concept (i), we investigated the adsorption geometry and isomerization behavior of various molecular switches on metal substrates which are able to undergo a photoinduced trans/cis-isomerization in solution. We investigated three isoelectronic molecules on Au where we systematically changed the photochemically active group from the diazo-group in an azobenzene-derivative (on Cu(111)) to the imine-group, and the vinylene-group, respectively. Finding the photoisomerization quenched for all systems we observed considerable differences in their thermal isomerization behavior. Comparable we find the photoinduced ring-opening/closing-reaction of spiropyran quenched on Au(111) but a thermally induced ring-opening reaction resulting in the open form being strongly stabilized by the metal. SFG spectroscopy is employed to investigate the reversible, photoinduced trans/cis-isomerization of an azobenzene-functionalized self-assembled monolayer (SAM) on gold using a tripodal linker system. In consequence of the decoupling provided by the tripodal linker, the switching behavior of the

  19. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding

    NARCIS (Netherlands)

    Ruger, R.; Niehaus, T.; van Lenthe, E.; Heine, T.; Visscher, L.

    2016-01-01

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nu- clear wavefunction.

  20. Distinguishing Nitro vs Nitrito Coordination in Cytochrome c' Using Vibrational Spectroscopy and Density Functional Theory.

    Science.gov (United States)

    Nilsson, Zach N; Mandella, Brian L; Sen, Kakali; Kekilli, Demet; Hough, Michael A; Moënne-Loccoz, Pierre; Strange, Richard W; Andrew, Colin R

    2017-11-06

    Nitrite coordination to heme cofactors is a key step in the anaerobic production of the signaling molecule nitric oxide (NO). An ambidentate ligand, nitrite has the potential to coordinate via the N- (nitro) or O- (nitrito) atoms in a manner that can direct its reactivity. Distinguishing nitro vs nitrito coordination, along with the influence of the surrounding protein, is therefore of particular interest. In this study, we probed Fe(III) heme-nitrite coordination in Alcaligenes xylosoxidans cytochrome c' (AXCP), an NO carrier that excludes anions in its native state but that readily binds nitrite (K d ∼ 0.5 mM) following a distal Leu16 → Gly mutation to remove distal steric constraints. Room-temperature resonance Raman spectra (407 nm excitation) identify ν(Fe-NO 2 ), δ(ONO), and ν s (NO 2 ) nitrite ligand vibrations in solution. Illumination with 351 nm UV light results in photoconversion to {FeNO} 6 and {FeNO} 7 states, enabling FTIR measurements to distinguish ν s (NO 2 ) and ν as (NO 2 ) vibrations from differential spectra. Density functional theory calculations highlight the connections between heme environment, nitrite coordination mode, and vibrational properties and confirm that nitrite binds to L16G AXCP exclusively through the N atom. Efforts to obtain the nitrite complex crystal structure were hampered by photochemistry in the X-ray beam. Although low dose crystal structures could be modeled with a mixed nitrite (nitro)/H 2 O distal population, their photosensitivity and partial occupancy underscores the value of the vibrational approach. Overall, this study sheds light on steric determinants of heme-nitrite binding and provides vibrational benchmarks for future studies of heme protein nitrite reactions.

  1. spectroscopy

    African Journals Online (AJOL)

    Aghomotsegin

    2015-10-14

    Oct 14, 2015 ... characterized by using phenotypic, API and Fourier transform infrared (FTIR) spectroscopy methods. One hundred and fifty-seven (157) strains were isolated from 13 cheese samples, and identification test was performed for 83 strains. At the end of the study, a total of 22 Lactococcus sp., 36 Enterecoccus ...

  2. A tubular dielectric elastomer actuator: Fabrication, characterization and active vibration isolation

    DEFF Research Database (Denmark)

    Sarban, R.; Jones, R. W.; Mace, B. R.

    2011-01-01

    This contribution reviews the fabrication, characterization and active vibration isolation performance of a core-free rolled tubular dielectric elastomer (DE) actuator, which has been designed and developed by Danfoss PolyPower A/S. PolyPower DE material, PolyPower (TM), is produced in thin sheets...... of 80 mu m thickness with corrugated metallic electrodes on both sides. Tubular actuators are manufactured by rolling the DE sheets in a cylindrical shape. The electromechanical characteristics of such actuators are modeled based on equilibrium pressure equation. The model is validated with experimental...... the dominant dynamic characteristics of the core-free tubular actuator. It has been observed that all actuators have similar dynamic characteristics in a frequency range up to 1 kHz. A tubular actuator is then used to provide active vibration isolation (AVI) of a 250 g mass subject to shaker generated 'ground...

  3. Vibrating-Wire, Supercooled Liquid Water Content Sensor Calibration and Characterization Progress

    Science.gov (United States)

    King, Michael C.; Bognar, John A.; Guest, Daniel; Bunt, Fred

    2016-01-01

    NASA conducted a winter 2015 field campaign using weather balloons at the NASA Glenn Research Center to generate a validation database for the NASA Icing Remote Sensing System. The weather balloons carried a specialized, disposable, vibrating-wire sensor to determine supercooled liquid water content aloft. Significant progress has been made to calibrate and characterize these sensors. Calibration testing of the vibrating-wire sensors was carried out in a specially developed, low-speed, icing wind tunnel, and the results were analyzed. The sensor ice accretion behavior was also documented and analyzed. Finally, post-campaign evaluation of the balloon soundings revealed a gradual drift in the sensor data with increasing altitude. This behavior was analyzed and a method to correct for the drift in the data was developed.

  4. Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira, E-mail: mkhalil@chem.washington.edu [Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195 (United States)

    2014-02-28

    Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectra of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.

  5. Support Effects in Catalysis Studied by in-situ Sum Frequency Generation Vibrational Spectroscopy and in-situ X-Ray Spectroscopies

    Science.gov (United States)

    Kennedy, Griffin John

    Kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst. In order to establish a paradigm for metal-support interactions using colloidally synthesized Pt nanoparticles the ability of the organic capping agent to inhibit reactivity and interaction with the support must first be assessed. Pt nanoparticles capped by poly(vinylpyrrolidone) (PVP), and those from which the PVP is removed by UV light exposure, are investigated for two reactions, the hydrogenation of ethylene and the oxidation of methanol. It is shown that prior to PVP removal the particles are moderately active for both reactions. Following removal, the activity for the two reactions diverges, the ethylene hydrogenation rate increases 10-fold, while the methanol oxidation rate decreases 3-fold. To better understand this effect the capping agent prior to, and the residual carbon remaining after UV treatment are probed by sum frequency generation vibrational spectroscopy. Prior to removal no major differences are observed when the particles are exposed to alternating H2 and O2 environments. When the PVP is removed, carbonaceous fragments remain on the surface that dynamically restructure in H2 and O2. These fragments create a tightly bound shell in an oxygen environment and a porous coating of hydrogenated carbon in the hydrogen environment. Reaction rate measurements of thermally cleaned PVP and oleic acid capped particles show this effect to be independent of cleaning method or capping agent. In all this demonstrates the ability of the capping agent to mediate nanoparticle catalysis

  6. Vibrational Spectroscopy and Gas-Phase Thermochemistry of the Model Dipeptide N-Acetyl Glycine Methyl Amide

    Science.gov (United States)

    Leavitt, Christopher; Raston, Paul; Moody, Grant; Shirley, Caitlyne; Douberly, Gary

    2014-06-01

    The structure-function relationship in proteins is widely recognized, motivating numerous investigations of isolated neutral and ionic polypeptides that generally employ conformation specific, multidimensional UV and IR spectroscopies. This data taken in conjunction with computed harmonic frequencies has provided a snapshot of the underlying molecular physics at play in many polypeptides, but few experiments have been able to probe the energetics of these systems. In this study, we use vibrational spectroscopy to measure the gas-phase enthalpy change for isomerization between two conformations of the dipeptide N-acetyl glycine methyl amide (NAGMA). A two-stage oven source is implemented producing a gas-phase equilibrium distribution of NAGMA molecules that is flash frozen upon pickup by He nanodroplets. Using polarization spectroscopy, the IR spectrum is assigned to a mixture of two conformers having intramolecular hydrogen bonds made up of either five- or seven-membered rings, C5 and C7, respectively. The interconversion enthalpy, obtained from the van't Hoff relation, is 4.52{±}0.12 kJ/mol for isomerization from the C7 to the C5-conformer. This experimental measurement is compared to computations employing a broad range of theoretical methods.

  7. Does ℏ play a role in multidimensional spectroscopy? Reduced hierarchy equations of motion approach to molecular vibrations.

    Science.gov (United States)

    Sakurai, Atsunori; Tanimura, Yoshitaka

    2011-04-28

    To investigate the role of quantum effects in vibrational spectroscopies, we have carried out numerically exact calculations of linear and nonlinear response functions for an anharmonic potential system nonlinearly coupled to a harmonic oscillator bath. Although one cannot carry out the quantum calculations of the response functions with full molecular dynamics (MD) simulations for a realistic system which consists of many molecules, it is possible to grasp the essence of the quantum effects on the vibrational spectra by employing a model Hamiltonian that describes an intra- or intermolecular vibrational motion in a condensed phase. The present model fully includes vibrational relaxation, while the stochastic model often used to simulate infrared spectra does not. We have employed the reduced quantum hierarchy equations of motion approach in the Wigner space representation to deal with nonperturbative, non-Markovian, and nonsecular system-bath interactions. Taking the classical limit of the hierarchy equations of motion, we have obtained the classical equations of motion that describe the classical dynamics under the same physical conditions as in the quantum case. By comparing the classical and quantum mechanically calculated linear and multidimensional spectra, we found that the profiles of spectra for a fast modulation case were similar, but different for a slow modulation case. In both the classical and quantum cases, we identified the resonant oscillation peak in the spectra, but the quantum peak shifted to the red compared with the classical one if the potential is anharmonic. The prominent quantum effect is the 1-2 transition peak, which appears only in the quantum mechanically calculated spectra as a result of anharmonicity in the potential or nonlinearity of the system-bath coupling. While the contribution of the 1-2 transition is negligible in the fast modulation case, it becomes important in the slow modulation case as long as the amplitude of the

  8. Analysis of carboxylate coordination function of the isomeric lanthanide pyridinedicarboxylates by means of vibration spectroscopy

    International Nuclear Information System (INIS)

    Puntus, L.; Zolin, V.; Kudryashova, V.

    2004-01-01

    The investigation of IR spectra of salts of six isomers of pyridinedicarboxylic acid (PDA): 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinedicarboxylic acids, have demonstrated that properties of these salts are dependent on the bonding manner of carboxylate groups and on coordination of heterocyclic nitrogen atom. The most prominent differences in properties and spectra of 2,6- and 3,4-PDA salts are conditioned correspondingly by monodentate and bidentate coordination functions of the carboxylate groups in these compounds. The correlation of the breathing vibration frequency, reflecting the rigidity of the heterocyclic ring, with position of the carboxylate substituents, conditioning intramolecular charge transfer (CT), was postulated and proved by shifts of the breathing vibration frequency dependent on the structure of isomeric ligand

  9. Analysis of solid-state transformations of pharmaceutical compounds using vibrational spectroscopy

    DEFF Research Database (Denmark)

    Heinz, Andrea; Strachan, Clare J; Gordon, Keith C

    2009-01-01

    OBJECTIVES: Solid-state transformations may occur during any stage of pharmaceutical processing and upon storage of a solid dosage form. Early detection and quantification of these transformations during the manufacture of solid dosage forms is important since the physical form of an active...... pharmaceutical ingredient can significantly influence its processing behaviour, including powder flow and compressibility, and biopharmaceutical properties such as solubility, dissolution rate and bioavailability. KEY FINDINGS: Vibrational spectroscopic techniques such as infrared, near-infrared, Raman and, most...... multivariate approaches where even overlapping spectral bands can be analysed. SUMMARY: This review discusses the applications of different vibrational spectroscopic techniques to detect and monitor solid-state transformations possible for crystalline polymorphs, hydrates and amorphous forms of pharmaceutical...

  10. Determining the Absolute Configuration of Two Marine Compounds Using Vibrational Chiroptical Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Hopmann, K. H.; Šebestík, Jaroslav; Novotná, J.; Stensen, W.; Urbanová, M.; Svenson, J.; Svendsen, J. S.; Bouř, Petr; Ruud, K.

    2012-01-01

    Roč. 77, č. 2 (2012), s. 858-869 ISSN 0022-3263 R&D Projects: GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Institutional research plan: CEZ:AV0Z40550506 Keywords : vibrational circular dichroism * Raman optical activity * absolute configuration * bioprospecting Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.564, year: 2012

  11. The Composition of Intermediate Products of the Thermal Decomposition of (NH4)2ZrF6 to ZrO2 from Vibrational-Spectroscopy Data

    Science.gov (United States)

    Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.

    2018-03-01

    Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.

  12. A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kneebone, Jared L. [Univ. of Rochester, Rochester, NY (United States); Daifuku, Stephanie L. [Univ. of Rochester, Rochester, NY (United States); Kehl, Jeffrey A. [Univ. of Rochester, Rochester, NY (United States); Wu, Gang [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chung, Hoon T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hu, Michael Y. [Argonne National Lab. (ANL), Argonne, IL (United States); Alp, E. Ercan [Argonne National Lab. (ANL), Argonne, IL (United States); More, Karren L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zelenay, Piotr [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Neidig, Michael L. [Univ. of Rochester, Rochester, NY (United States)

    2017-07-06

    While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O2 or O2-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO(g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO(g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO(g) probe molecules. Moreover, such sites are likely also reactive to O2, possibly serving as the ORR active sites in the synthesized materials.

  13. Description of pnicogen bonding with the help of vibrational spectroscopy-The missing link between theory and experiment

    Science.gov (United States)

    Setiawan, D.; Kraka, E.; Cremer, D.

    2014-10-01

    The nature of the E⋯E‧ pnicogen bond (E = N, P, As) in dimers such as H2FP⋯PH2F (1) and H3N⋯PHNO2 (2) can be described using vibrational spectroscopy in form of the calculated infrared and depolarized Raman scattering spectra. Utilizing the six calculated intermonomer frequencies, the corresponding local mode E⋯E‧ stretching frequency and force constant are obtained, where the latter provides a unique measure of the E⋯E‧ bond strength. Pnicogen bonding in 1 is relative strong (bond strength order n = 0.151) and covalent whereas pnicogen bonding in 2 is electrostatic (n = 0.047) because of a different bonding mechanism.

  14. Conformational analysis of quinine and its pseudo enantiomer quinidine: a combined jet-cooled spectroscopy and vibrational circular dichroism study.

    Science.gov (United States)

    Sen, Ananya; Bouchet, Aude; Lepère, Valeria; Le Barbu-Debus, Katia; Scuderi, D; Piuzzi, F; Zehnacker-Rentien, A

    2012-08-16

    Laser-desorbed quinine and quinidine have been studied in the gas phase by combining supersonic expansion with laser spectroscopy, namely, laser-induced fluorescence (LIF), resonance-enhanced multiphoton ionization (REMPI), and IR-UV double resonance experiments. Density funtional theory (DFT) calculations have been done in conjunction with the experimental work. The first electronic transition of quinine and quinidine is of π-π* nature, and the studied molecules weakly fluoresce in the gas phase, in contrast to what was observed in solution (Qin, W. W.; et al. J. Phys. Chem. C2009, 113, 11790). The two pseudo enantiomers quinine and quinidine show limited differences in the gas phase; their main conformation is of open type as it is in solution. However, vibrational circular dichroism (VCD) experiments in solution show that additional conformers exist in condensed phase for quinidine, which are not observed for quinine. This difference in behavior between the two pseudo enantiomers is discussed.

  15. Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

    Science.gov (United States)

    Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

    2016-04-26

    Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

  16. Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods.

    Science.gov (United States)

    Barnette, Anna L; Lee, Christopher; Bradley, Laura C; Schreiner, Edward P; Park, Yong Bum; Shin, Heenae; Cosgrove, Daniel J; Park, Sunkyu; Kim, Seong H

    2012-07-01

    The non-centrosymmetry requirement of sum frequency generation (SFG) vibration spectroscopy allows the detection and quantification of crystalline cellulose in lignocellulose biomass without spectral interferences from hemicelluloses and lignin. This paper shows a correlation between the amount of crystalline cellulose in biomass and the SFG signal intensity. Model biomass samples were prepared by mixing commercially available cellulose, xylan, and lignin to defined concentrations. The SFG signal intensity was found sensitive to a wide range of crystallinity, but varied non-linearly with the mass fraction of cellulose in the samples. This might be due to the matrix effects such as light scattering and absorption by xylan and lignin, as well as the non-linear density dependence of the SFG process itself. Comparison with other techniques such as XRD, FT-Raman, FT-IR and NMR demonstrate that SFG can be a complementary and sensitive tool to assess crystalline cellulose in biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Characterization and discrimination of human breast cancer and normal breast tissues using resonance Raman spectroscopy

    Science.gov (United States)

    Wu, Binlin; Smith, Jason; Zhang, Lin; Gao, Xin; Alfano, Robert R.

    2018-02-01

    Worldwide breast cancer incidence has increased by more than twenty percent in the past decade. It is also known that in that time, mortality due to the affliction has increased by fourteen percent. Using optical-based diagnostic techniques, such as Raman spectroscopy, has been explored in order to increase diagnostic accuracy in a more objective way along with significantly decreasing diagnostic wait-times. In this study, Raman spectroscopy with 532-nm excitation was used in order to incite resonance effects to enhance Stokes Raman scattering from unique biomolecular vibrational modes. Seventy-two Raman spectra (41 cancerous, 31 normal) were collected from nine breast tissue samples by performing a ten-spectra average using a 500-ms acquisition time at each acquisition location. The raw spectral data was subsequently prepared for analysis with background correction and normalization. The spectral data in the Raman Shift range of 750- 2000 cm-1 was used for analysis since the detector has highest sensitivity around in this range. The matrix decomposition technique nonnegative matrix factorization (NMF) was then performed on this processed data. The resulting leave-oneout cross-validation using two selective feature components resulted in sensitivity, specificity and accuracy of 92.6%, 100% and 96.0% respectively. The performance of NMF was also compared to that using principal component analysis (PCA), and NMF was shown be to be superior to PCA in this study. This study shows that coupling the resonance Raman spectroscopy technique with subsequent NMF decomposition method shows potential for high characterization accuracy in breast cancer detection.

  18. Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy

    Science.gov (United States)

    Maekawa, Hiroaki; Sul, Soohwan; Ge, Nien-Hui

    2013-08-01

    We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester Cdbnd O and diazo Ndbnd N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency-frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single Cdbnd O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anticorrelated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed.

  19. Using vibrational molecular spectroscopy to reveal association of steam-flaking induced carbohydrates molecular structural changes with grain fractionation, biodigestion and biodegradation

    Science.gov (United States)

    Xu, Ningning; Liu, Jianxin; Yu, Peiqiang

    2018-04-01

    Advanced vibrational molecular spectroscopy has been developed as a rapid and non-destructive tool to reveal intrinsic molecular structure conformation of biological tissues. However, this technique has not been used to systematically study flaking induced structure changes at a molecular level. The objective of this study was to use vibrational molecular spectroscopy to reveal association between steam flaking induced CHO molecular structural changes in relation to grain CHO fractionation, predicted CHO biodegradation and biodigestion in ruminant system. The Attenuate Total Reflectance Fourier-transform Vibrational Molecular Spectroscopy (ATR-Ft/VMS) at SRP Key Lab of Molecular Structure and Molecular Nutrition, Ministry of Agriculture Strategic Research Chair Program (SRP, University of Saskatchewan) was applied in this study. The fractionation, predicted biodegradation and biodigestion were evaluated using the Cornell Net Carbohydrate Protein System. The results show that: (1) The steam flaking induced significant changes in CHO subfractions, CHO biodegradation and biodigestion in ruminant system. There were significant differences between non-processed (raw) and steam flaked grain corn (P R2 = 0.87, RSD = 0.74, P R2 = 0.87, RSD = 0.24, P < .01). In summary, the processing induced molecular CHO structure changes in grain corn could be revealed by the ATR-Ft/VMS vibrational molecular spectroscopy. These molecular structure changes in grain were potentially associated with CHO biodegradation and biodigestion.

  20. Structure and Absolute Configuration of Nyasol and Hinokiresinol via Synthesis and Vibrational Circular Dichroism Spectroscopy

    DEFF Research Database (Denmark)

    Lassen, Peter Rygaard

    2005-01-01

    The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol...... enables establishment of the absolute configuration of (-)-hinokiresinol, which is concluded to be S. A total synthesis and resolution of hinokiresinol has been performed to resolve the conflicting reports of the coupling constant of the vinylic protons of the disubstituted double bond in this molecule...

  1. Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

    Science.gov (United States)

    Vidal, F.; Busson, B.; Tadjeddine, A.

    2005-02-01

    We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

  2. Moessbauer spectroscopy characterization of Zr-Nb-Fe phases

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, C.P. [CONICET, Av. Gral. Paz 1499, 1650 Buenos Aires (Argentina)]. E-mail: ciramos@cnea.gov.ar; Granovsky, M.S. [CAC-CNEA, Av. Gral. Paz 1499, 1650 Buenos Aires (Argentina); Saragovi, C. [CAC-CNEA, Av. Gral. Paz 1499, 1650 Buenos Aires (Argentina)

    2007-02-01

    The aim of this work was the characterization of the ternary phases and of those coming from the corresponding binary systems in the Zr-Nb-Fe diagram by means of Moessbauer spectroscopy. This is part of a complete study involving a tentative isothermal section at 900 deg. C of the center of the Zr-Nb-Fe diagram which will be published elsewhere. Zr-Nb-Fe alloys with Nb contents between 5 and 50 at% and Fe contents between 10 and 60 at% were analyzed after a heat treatment at 900 deg. C for 4 month. Moessbauer characterization of the phases was complemented by optical and scanning electron microscopies, X-ray diffraction and electron microprobe analysis. From the obtained results it can be inferred that Fe in both of the Laves phases present in this system (Zr(FeNb){sub 2} and (ZrNb)Fe{sub 2}) sees different environments, producing quadrupole splitting and hyperfine field distributions, respectively. Two types of body centered cubic {beta} phases (Zr-rich and Nb-rich) were found having noticeable differences in their Moessbauer parameters. Furthermore it was shown that the ternary Fe(NbZr){sub 2} compound would show magnetic character at low temperatures. Concentration dependence of the hyperfine parameters and their relations with the lattice parameters contributed to the structural characterization of the phases.

  3. Moessbauer spectroscopy characterization of Zr-Nb-Fe phases

    International Nuclear Information System (INIS)

    Ramos, C.P.; Granovsky, M.S.; Saragovi, C.

    2007-01-01

    The aim of this work was the characterization of the ternary phases and of those coming from the corresponding binary systems in the Zr-Nb-Fe diagram by means of Moessbauer spectroscopy. This is part of a complete study involving a tentative isothermal section at 900 deg. C of the center of the Zr-Nb-Fe diagram which will be published elsewhere. Zr-Nb-Fe alloys with Nb contents between 5 and 50 at% and Fe contents between 10 and 60 at% were analyzed after a heat treatment at 900 deg. C for 4 month. Moessbauer characterization of the phases was complemented by optical and scanning electron microscopies, X-ray diffraction and electron microprobe analysis. From the obtained results it can be inferred that Fe in both of the Laves phases present in this system (Zr(FeNb) 2 and (ZrNb)Fe 2 ) sees different environments, producing quadrupole splitting and hyperfine field distributions, respectively. Two types of body centered cubic β phases (Zr-rich and Nb-rich) were found having noticeable differences in their Moessbauer parameters. Furthermore it was shown that the ternary Fe(NbZr) 2 compound would show magnetic character at low temperatures. Concentration dependence of the hyperfine parameters and their relations with the lattice parameters contributed to the structural characterization of the phases

  4. Characterization of defects in metals by positron-annihilation spectroscopy

    International Nuclear Information System (INIS)

    Siegel, R.W.

    1981-10-01

    The application of positron-annihilation spectroscopy (PAS) to the characterization and study of defects in metals has grown rapidly and increasingly useful in recent years. Owing to the ability of the positron to annihilate from a variety of defect-trapped states in metals, PAS can yield defect-specific information which, by itself or in conjunction with more traditional experimental techniques, has already made a significant impact upon our knowledge regarding lattice defect properties in metals. This has been especially true for vacancy defets, as a result of the positron's affinity for lower-than-average electron-density regions in the metal. The physical basis for the positron annihilation techniques is presented in this paper; and the experimental techniques, lifetime, Doppler broadening, and angular correlation, are briefly described and compared with respect to the information that can be obtained from each of them. A number of examples of the application of PAS to the characterization of atomic defects and their agglomerates are presented. The particular examples, chosen from the areas of equilibrium vacancy formation and atomic-defect recovery, were selected with a view toward elucidating the particular advantages of PAS over more traditional defect-characterization techniques. Limitations of PAS are also pointed out. 98 references

  5. Cell growth characterization using multi-electrode bioimpedance spectroscopy

    International Nuclear Information System (INIS)

    Lu, Yi-Yu; Huang, Yu-Jie; Cheng, Kuo-Sheng; Huang, Ji-Jer

    2013-01-01

    Cell growth characterization during culturing is an important issue in a variety of biomedical applications. In this study an electrical bioimpedance spectroscopy-based multi-electrode culture monitoring system was developed to characterize cell growth. A PC12 cell line was cultured for the cell growth study. The bioimpedance variations for PC12 cell growth within the initial 12 h were measured over a range between 1 kHz and 4 MHz at three different medium concentrations. Within this frequency range, the largest bioimpedance value was 1.9 times the smallest bioimpedance value. The phase angle decreased over the range from 1 to 10 kHz when cells were growing. Then, the phase angle approached a constant over the frequency range between 10 kHz and 2 MHz. Thereafter, the phase angle increased rapidly from 20 to 52 degrees during cell culturing between 8 and 12 h at 4 MHz. The maximum cell number after culturing for 12 h increased by 25.8% for the control sites with poly-D-lysine (PDL) pastes. For the normal growth factor, the cell number increased up to 4.78 times from 8 to 12 h, but only 0.96 and 1.60 times for the other two medium growth factors. The correlation coefficients between impedance and cell number were 0.868 (coating with PDL), and 0.836 (without PDL) for the normal concentration medium. Thus, impedance may be used as an index for cell growth characterization. (paper)

  6. A complete vibrational study on a potential environmental toxicant agent, the 3,3',4,4'-tetrachloroazobenzene combining the FTIR, FTRaman, UV-Visible and NMR spectroscopies with DFT calculations.

    Science.gov (United States)

    Castillo, María V; Pergomet, Jorgelina L; Carnavale, Gustavo A; Davies, Lilian; Zinczuk, Juan; Brandán, Silvia A

    2015-01-05

    In this study 3,3',4,4'-tetrachloroazobenzene (TCAB) was prepared and then characterized by infrared, Raman, multidimensional nuclear magnetic resonance (NMR) and ultraviolet-visible spectroscopies. The density functional theory (DFT) together with the 6-31G(*) and 6-311++G(**) basis sets were used to study the structures and vibrational properties of the two cis and trans isomers of TCAB. The harmonic vibrational wavenumbers for the optimized geometries were calculated at the same theory levels. A complete assignment of all the observed bands in the vibrational spectra of TCAB was performed combining the DFT calculations with the scaled quantum mechanical force field (SQMFF) methodology. The molecular electrostatic potentials, atomic charges, bond orders and frontier orbitals for the two isomers of TCAB were compared and analyzed. The comparison of the theoretical ultraviolet-visible spectrum with the corresponding experimental demonstrates a good concordance while the calculated (1)H and (13)C chemicals shifts are in good conformity with the corresponding experimental NMR spectra of TCAB in solution. The npp(*) transitions for both forms were studied by natural bond orbital (NBO) while the topological properties were calculated by employing Bader's Atoms in the Molecules (AIM) theory. This study shows that the cis and trans isomers exhibit different structural and vibrational properties and absorption bands. Copyright © 2014. Published by Elsevier B.V.

  7. Characterization of CdSe polycrystalline films by photoluminescence spectroscopy

    International Nuclear Information System (INIS)

    Brasil, M.J.S.P.

    1985-01-01

    The characterization of CdSe polycristalline films were done by photoluminescence spectroscopy, X-ray diffraction analysis, diagrams IxV, and efficiency of solar energy conversion for cells done by these films. The experimental data shown strong temperature dependence of annealing, and the optimum temperature around 650 0 C was determined. The films did not present photoluminescence before heat treatment, but the annealed sample spectrum showed fine structures in the excitonic region, crystal phase transformation, enhancement of grain size, and better efficiency of the cell. Measurements of photoluminescence between 2 and 300 K, showed two bands of infrared emission, width and intense enough. The shape, at half-width, and the integrated intensity of one these bands were described by a configuration coordinate model for deep centers. Based on obtained results, some hypothesis about the origin of these bands and its correlation with efficiency of cells done with CdSe polycrystalline films, are proposed. (M.C.K.) [pt

  8. Using Rutherford Backscattering Spectroscopy to Characterize Targets for MTW

    Science.gov (United States)

    Brown, Gunnar; Stockler, Barak; Ward, Ryan; Freeman, Charlie; Padalino, Stephen; Stillman, Collin; Ivancic, Steven; Reagan, S. P.; Sangster, T. C.

    2017-10-01

    A study is underway to determine the composition and thickness of targets used at the Multiterawatt (MTW) laser facility at the Laboratory for Laser Energetics (LLE) using Rutherford backscattering spectroscopy (RBS). In RBS, an ion beam is incident on a sample and the scattered ions are detected with a surface barrier detector. The resulting energy spectra of the scattered ions can be analyzed to determine important parameters of the target including elemental composition and thickness. Proton, helium and deuterium beams from the 1.7 MV Pelletron accelerator at SUNY Geneseo have been used to characterize several different targets for MTW, including CH and aluminum foils of varying thickness. RBS spectra were also obtained for a cylindrical iron buried-layer target with aluminum dopant which was mounted on a silicon carbide stalk. The computer program SIMNRA is used to analyze the spectra. This work was funded in part by a Grant from the DOE through the Laboratory for Laser Energetics.

  9. Difference frequency generation spectroscopy as a vibrational optical activity measurement tool.

    Science.gov (United States)

    Cheon, Sangheon; Cho, Minhaeng

    2009-03-19

    Vibrational optical activity (VOA) of chiral molecules in condensed phases can be studied by using vibrational circular dichroism and Raman optical activity measurement techniques. Recently, IR-vis sum frequency generation has shown to be an alternative VOA measurement method. Such a three-wave-mixing method employing a polarization modulation technique can be a potentially useful VOA measurement tool. Here, a theoretical description of difference frequency generation (DFG) employing circularly polarized visible radiations is presented. Frequency scanning to obtain a VOA-DFG spectrum is achieved by controlling the difference between the two electronically nonresonant incident radiation frequencies. If the two incident beams are linearly polarized and their polarization directions are perpendicular to each other, one can selectively measure the all-electric-dipole-allowed chiral component of the DFG susceptibility. In addition, by using circularly polarized beams and taking the DFG difference intensity signal, which is defined as the difference between left and right circularly polarized DFG signals, additional chiral susceptibility components originating from the electric quadrupole transition can be measured. The DFG as a novel VOA measurement technique for solution samples containing chiral molecules will therefore be a useful coherent spectroscopic tool for determining absolute configuration of chiral molecules in condensed phases.

  10. Vibrational spectroscopy and chemometrics for rapid, quantitative analysis of bitter acids in hops (Humulus lupulus).

    Science.gov (United States)

    Killeen, Daniel P; Andersen, David H; Beatson, Ron A; Gordon, Keith C; Perry, Nigel B

    2014-12-31

    Hops, Humulus lupulus, are grown worldwide for use in the brewing industry to impart characteristic flavor and aroma to finished beer. Breeders produce many varietal crosses with the aim of improving and diversifying commercial hops varieties. The large number of crosses critical to a successful breeding program imposes high demands on the supporting chemical analytical laboratories. With the aim of reducing the analysis time associated with hops breeding, quantitative partial least-squares regression (PLS-R) models have been produced, relating reference data acquired by the industrial standard HPLC and UV methods, to vibrational spectra of the same, chemically diverse hops sample set. These models, produced from rapidly acquired infrared (IR), near-infrared (NIR), and Raman spectra, were appraised using standard statistical metrics. Results demonstrated that all three spectroscopic methods could be used for screening hops for α-acid, total bitter acids, and cohumulone concentrations in powdered hops. Models generated from Raman and IR spectra also showed potential for use in screening hops varieties for xanthohumol concentrations. NIR analysis was performed using both a standard benchtop spectrometer and a portable NIR spectrometer, with comparable results obtained by both instruments. Finally, some important vibrational features of cohumulone, colupulone, and xanthohumol were assigned using DFT calculations, which allow more insightful interpretation of PLS-R latent variable plots.

  11. Benchmarking fully analytic DFT force fields for vibrational spectroscopy: A study on halogenated compounds

    Science.gov (United States)

    Pietropolli Charmet, Andrea; Cornaton, Yann

    2018-05-01

    This work presents an investigation of the theoretical predictions yielded by anharmonic force fields having the cubic and quartic force constants are computed analytically by means of density functional theory (DFT) using the recursive scheme developed by M. Ringholm et al. (J. Comput. Chem. 35 (2014) 622). Different functionals (namely B3LYP, PBE, PBE0 and PW86x) and basis sets were used for calculating the anharmonic vibrational spectra of two halomethanes. The benchmark analysis carried out demonstrates the reliability and overall good performances offered by hybrid approaches, where the harmonic data obtained at the coupled cluster with single and double excitations level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T), are combined with the fully analytic higher order force constants yielded by DFT functionals. These methods lead to reliable and computationally affordable calculations of anharmonic vibrational spectra with an accuracy comparable to that yielded by hybrid force fields having the anharmonic force fields computed at second order Møller-Plesset perturbation theory (MP2) level of theory using numerical differentiation but without the corresponding potential issues related to computational costs and numerical errors.

  12. Rotation and rotation-vibration spectroscopy of the 0+-0- inversion doublet in deuterated cyanamide.

    Science.gov (United States)

    Kisiel, Zbigniew; Kraśnicki, Adam; Jabs, Wolfgang; Herbst, Eric; Winnewisser, Brenda P; Winnewisser, Manfred

    2013-10-03

    The pure rotation spectrum of deuterated cyanamide was recorded at frequencies from 118 to 649 GHz, which was complemented by measurement of its high-resolution rotation-vibration spectrum at 8-350 cm(-1). For D2NCN the analysis revealed considerable perturbations between the lowest Ka rotational energy levels in the 0(+) and 0(-) substates of the lowest inversion doublet. The final data set for D2NCN exceeded 3000 measured transitions and was successfully fitted with a Hamiltonian accounting for the 0(+) ↔ 0(-) coupling. A smaller data set, consisting only of pure rotation and rotation-vibration lines observed with microwave techniques was obtained for HDNCN, and additional transitions of this type were also measured for H2NCN. The spectroscopic data for all three isotopic species were fitted with a unified, robust Hamiltonian allowing confident prediction of spectra well into the terahertz frequency region, which is of interest to contemporary radioastronomy. The isotopic dependence of the determined inversion splitting, ΔE = 16.4964789(8), 32.089173(3), and 49.567770(6) cm(-1), for D2NCN, HDNCN, and H2NCN, respectively, is found to be in good agreement with estimates from a simple reduced quartic-quadratic double minimum potential.

  13. Femtosecond time-resolved vibrational SFG spectroscopy of CO/Ru( 0 0 1 )

    Science.gov (United States)

    Hess, Ch.; Wolf, M.; Roke, S.; Bonn, M.

    2002-04-01

    Vibrational sum-frequency generation (SFG) employing femtosecond infrared (IR) laser pulses is used to study the dynamics of the C-O stretch vibration on Ru(0 0 1). Time-resolved measurements of the free induction decay (FID) of the IR-polarization for 0.33 ML CO/Ru(0 0 1) exhibit single exponential decays over three decades corresponding to dephasing times of T2=1.94 ps at 95 K and T2=1.16 ps at 340 K. This is consistent with pure homogeneous broadening due to anharmonic coupling with the thermally activated low-frequency dephasing mode together with a contribution from saturation of the IR transition. In pump-probe SFG experiments using a strong visible (VIS) pump pulse the perturbation of the FID leads to transient line shifts even at negative delay times, i.e. when the IR-VIS SFG probe pair precedes the pump pulse. Based on an analysis of the time-dependent polarization we discuss the influence of the perturbed FID on time-resolved SFG spectra. We investigate how coherent effects affect the SFG spectra and we examine the time resolution in these experiments, in particular in dependence of the dephasing time.

  14. Gold micro- and nano-particles for surface enhanced vibrational spectroscopy of pyridostigmine bromide

    DEFF Research Database (Denmark)

    Dolgov, Leonid; Fesenko, Olena; Kavelin, Vladyslav

    2017-01-01

    Triangular gold microprisms and spherical silica nanoparticles with attached gold nano-islands were examined as an active nanostructures for the surface enhanced Raman and infrared spectroscopy. These particles were probed for the detection of pyridostigmine bromide as a safe analog of military c...

  15. Screening Pinus taeda (loblolly pine) families for physical and mechanical properties using vibrational spectroscopy

    Science.gov (United States)

    Gifty E. Acquah; Brian K. Via; Lori G. Eckhardt

    2016-01-01

    In a bid to control the loblolly pine decline complex, stakeholders are using the selection and deployment of genetically superior families that are disease tolerant. It is vital that we do not compromise other important properties while breeding for disease tolerance. In this preliminary study, near infrared spectroscopy was utilized in conjunction with data collected...

  16. Localized corrosion evaluation of the ASTM F139 stainless steel marked by laser using scanning vibrating electrode technique, X-ray photoelectron spectroscopy and Mott–Schottky techniques

    International Nuclear Information System (INIS)

    Pieretti, Eurico F.; Manhabosco, Sara M.; Dick, Luís F.P.; Hinder, Steve; Costa, Isolda

    2014-01-01

    Graphical abstract: SEM image of pits found at the centred marked area, where the laser beam focused twice. - Highlights: • The effect of laser engraving on the corrosion resistance of the ASTM F139 was studied. • Scanning vibrating electrode technique was used to identify the anodic zone. • Laser engraving of austenitic stainless steels produces highly defective surfaces. • Laser engraving causes large chemical modification of the surface. • Pitting nucleates at the interface between laser affected and unaffected areas. - Abstract: The effect of laser engraving on the corrosion resistance of ASTM F139 stainless steel (SS) has been investigated by electrochemical techniques. The nucleation of localized corrosion on this biomaterial was evaluated by scanning vibrating electrode technique (SVET) in a phosphate buffered saline solution (PBS) of pH 7.4. The Mott–Schottky approach was used to determine the electronic properties of the passive film, also chemically characterized by X-ray photoelectron spectroscopy (XPS). SVET allowed the identification of the anodic zones on the surface of the SS marked by laser technique that were associated with the heat-affected areas. Metallic drops solidified on the laser marked surface dissolved actively at OCP and favoured the nucleation of crevice corrosion, while at the pitting potential, pits nucleate preferentially on the laser marks. XPS results showed that laser engraving caused large chemical modification of the surface. Mott–Schottky results indicated a more defective oxide layer with a larger number of donors on the laser marked surface comparatively to that without marks

  17. Spectral methods for study of the G-protein-coupled receptor rhodopsin: I. Vibrational and electronic spectroscopy

    Science.gov (United States)

    Struts, A. V.; Barmasov, A. V.; Brown, M. F.

    2015-05-01

    Here we review the application of modern spectral methods for the study of G-protein-coupled receptors (GPCRs) using rhodopsin as a prototype. Because X-ray analysis gives us immobile snapshots of protein conformations, it is imperative to apply spectroscopic methods for elucidating their function: vibrational (Raman, FTIR), electronic (UV-visible absorption, fluorescence) spectroscopies, and magnetic resonance (electron paramagnetic resonance, EPR), and nuclear magnetic resonance (NMR). In the first of the two companion articles, we discuss the application of optical spectroscopy for studying rhodopsin in a membrane environment. Information is obtained regarding the time-ordered sequence of events in rhodopsin activation. Isomerization of the chromophore and deprotonation of the retinal Schiff base leads to a structural change of the protein involving the motion of helices H5 and H6 in a pH-dependent process. Information is obtained that is unavailable from X-ray crystallography, which can be combined with spectroscopic studies to achieve a more complete understanding of GPCR function.

  18. Vibrational Properties of h-BN and h-BN-Graphene Heterostructures Probed by Inelastic Electron Tunneling Spectroscopy.

    Science.gov (United States)

    Jung, Suyong; Park, Minkyu; Park, Jaesung; Jeong, Tae-Young; Kim, Ho-Jong; Watanabe, Kenji; Taniguchi, Takashi; Ha, Dong Han; Hwang, Chanyong; Kim, Yong-Sung

    2015-11-13

    Inelastic electron tunneling spectroscopy is a powerful technique for investigating lattice dynamics of nanoscale systems including graphene and small molecules, but establishing a stable tunnel junction is considered as a major hurdle in expanding the scope of tunneling experiments. Hexagonal boron nitride is a pivotal component in two-dimensional Van der Waals heterostructures as a high-quality insulating material due to its large energy gap and chemical-mechanical stability. Here we present planar graphene/h-BN-heterostructure tunneling devices utilizing thin h-BN as a tunneling insulator. With much improved h-BN-tunneling-junction stability, we are able to probe all possible phonon modes of h-BN and graphite/graphene at Γ and K high symmetry points by inelastic tunneling spectroscopy. Additionally, we observe that low-frequency out-of-plane vibrations of h-BN and graphene lattices are significantly modified at heterostructure interfaces. Equipped with an external back gate, we can also detect high-order coupling phenomena between phonons and plasmons, demonstrating that h-BN-based tunneling device is a wonderful playground for investigating electron-phonon couplings in low-dimensional systems.

  19. Ribonuclease S dynamics measured using a nitrile label with 2D IR vibrational echo spectroscopy.

    Science.gov (United States)

    Bagchi, Sayan; Boxer, Steven G; Fayer, Michael D

    2012-04-05

    A nitrile-labeled amino acid, p-cyanophenylalanine, is introduced near the active site of the semisynthetic enzyme ribonuclease S to serve as a probe of protein dynamics and fluctuations. Ribonuclease S is the limited proteolysis product of subtilisin acting on ribonuclease A, and consists of a small fragment including amino acids 1-20, the S-peptide, and a larger fragment including residues 21-124, the S-protein. A series of two-dimensional vibrational echo experiments performed on the nitrile-labeled S-peptide and the RNase S are described. The time-dependent changes in the two-dimensional infrared vibrational echo line shapes are analyzed using the center line slope method to obtain the frequency-frequency correlation function (FFCF). The observations show that the nitrile probe in the S-peptide has dynamics that are similar to, but faster than, those of the single amino acid p-cyanophenylalanine in water. In contrast, the dynamics of the nitrile label when the peptide is bound to form ribonuclease S are dominated by homogeneous dephasing (motionally narrowed) contributions with only a small contribution from very fast inhomogeneous structural dynamics. The results provide insights into the nature of the structural dynamics of the ribonuclease S complex. The equilibrium dynamics of the nitrile labeled S-peptide and the ribonuclease S complex are also investigated by molecular dynamics simulations. The experimentally determined FFCFs are compared to the FFCFs obtained from the molecular dynamics simulations, thereby testing the capacity of simulations to determine the amplitudes and time scales of protein structural fluctuations on fast time scales under thermal equilibrium conditions.

  20. Fabrication and characterization of MEMS-based PZT/PZT bimorph thick film vibration energy harvesters

    DEFF Research Database (Denmark)

    Xu, Ruichao; Lei, Anders; Dahl-Petersen, Christian

    2012-01-01

    We describe the fabrication and characterization of a significantly improved version of a microelectromechanical system-based PZT/PZT thick film bimorph vibration energy harvester with an integrated silicon proof mass; the harvester is fabricated in a fully monolithic process. The main advantage...... yield of 98%. The robust fabrication process allowed a high pressure treatment of the screen printed PZT thick films prior to sintering. The high pressure treatment improved the PZT thick film performance and increased the harvester power output to 37.1 μW at 1 g root mean square acceleration. We also...... characterize the harvester performance when only one of the PZT layers is used while the other is left open or short circuit....

  1. Application of empirical mode decomposition method for characterization of random vibration signals

    Directory of Open Access Journals (Sweden)

    Setyamartana Parman

    2016-07-01

    Full Text Available Characterization of finite measured signals is a great of importance in dynamical modeling and system identification. This paper addresses an approach for characterization of measured random vibration signals where the approach rests on a method called empirical mode decomposition (EMD. The applicability of proposed approach is tested in one numerical and experimental data from a structural system, namely spar platform. The results are three main signal components, comprising: noise embedded in the measured signal as the first component, first intrinsic mode function (IMF called as the wave frequency response (WFR as the second component and second IMF called as the low frequency response (LFR as the third component while the residue is the trend. Band-pass filter (BPF method is taken as benchmark for the results obtained from EMD method.

  2. Synthesis, Characterization, and Spectroscopy of Model Molybdopterin Complexes‡

    Science.gov (United States)

    Burgmayer, Sharon J. Nieter; Kim, Mary; Petit, Rebecca; Rothkopf, Amy; Kim, Alison; BelHamdounia, Shadia; Hou, Ying; Somogyi, Arpad; Habel-Rodriguez, Diana; Williams, Antonio; Kirk, Martin L.

    2012-01-01

    The preparation and characterization of new model complexes for the molybdenum cofactor are reported. The new models are distinctive for the inclusion of pterin-substituted dithiolene chelates and have the formulation Tp*MoX(pterin-R-dithiolene) (Tp* = tris(3,5,-dimethylpyrazolyl)borate), X= O, S, R= aryl or −C(OH)(CH3)2). Syntheses of Mo(4+) and (5+) complexes of two pterin-dithiolene derivatives as both oxo and sulfido compounds, and improved syntheses for pterinyl alkynes and [Et4N][Tp*MoIV(S)S4] reagents are described. Characterization methods include electrospray ionization mass spectrometry, electrochemistry, infrared spectroscopy, electron paramagnetic resonance and magnetic circular dichroism. Cyclic voltammetry reveals that the Mo(5+/4+) reduction potential is intermediate between that for dithiolene with electron-withdrawing substituents and simple dithiolate chelates. Electron paramagnetic resonance and magnetic circular dichroism of Mo(5+) complexes where X = O, R = aryl indicates that the molybdenum environment in the new models is electronically similar to that in Tp*MoO(benzenedithiolate). PMID:17765313

  3. X-ray and vibrational spectroscopy of manganese complexes relevant to the oxygen-evolving complex of photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Visser, Hendrik [Univ. of California, Berkeley, CA (United States)

    2001-01-01

    Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation of IR spectra of Mn compounds in different oxidation states. The design, based on an attenuated total reflection device, permits the study of a wide spectral range: 16,700 (600 nm) - 225

  4. Ro-vibrational laser spectroscopy of ESD neutrals from chemisorbed species

    International Nuclear Information System (INIS)

    Burns, A.R.; Stechel, E.B.; Jennison, D.R.

    1987-01-01

    Ever since the introduction of intense tunable laser radiation, the fields of molecular spectroscopy and dynamics have expanded tremendously. Indeed, with each technical improvement in laser resolution and output power, new applications have emerged with correspondingly increased levels of sophistication and information. In the field of electron-stimulated desorption (ESD), not only has the utilization of lasers resulted in the detection of neutral species, which were previously difficult to observe without specially-designed analyzers, but also the quantum-specific nature of the resonant laser interaction with the neutrals has yielded valuable information concerning internal energies. In this article, we will discuss some of the experimental methods in the application of laser resonance-ionization spectroscopy (RIS) to the study of the ESD of neutrals, in particular, chemisorbed NO and CO desorption from Pt(111). We will also show how the detailed information obtained in these experiments has identified a new desorption mechanism

  5. Characterizing aeroallergens by infrared spectroscopy of fungal spores and pollen.

    Directory of Open Access Journals (Sweden)

    Boris Zimmermann

    Full Text Available Fungal spores and plant pollen cause respiratory diseases in susceptible individuals, such as asthma, allergic rhinitis and hypersensitivity pneumonitis. Aeroallergen monitoring networks are an important part of treatment strategies, but unfortunately traditional analysis is time consuming and expensive. We have explored the use of infrared spectroscopy of pollen and spores for an inexpensive and rapid characterization of aeroallergens.The study is based on measurement of spore and pollen samples by single reflectance attenuated total reflectance Fourier transform infrared spectroscopy (SR-ATR FTIR. The experimental set includes 71 spore (Basidiomycota and 121 pollen (Pinales, Fagales and Poales samples. Along with fresh basidiospores, the study has been conducted on the archived samples collected within the last 50 years.The spectroscopic-based methodology enables clear spectral differentiation between pollen and spores, as well as the separation of confamiliar and congeneric species. In addition, the analysis of the scattering signals inherent in the infrared spectra indicates that the FTIR methodology offers indirect estimation of morphology of pollen and spores. The analysis of fresh and archived spores shows that chemical composition of spores is well preserved even after decades of storage, including the characteristic taxonomy-related signals. Therefore, biochemical analysis of fungal spores by FTIR could provide economical, reliable and timely methodologies for improving fungal taxonomy, as well as for fungal identification and monitoring. This proof of principle study shows the potential for using FTIR as a rapid tool in aeroallergen studies. In addition, the presented method is ready to be immediately implemented in biological and ecological studies for direct measurement of pollen and spores from flowers and sporocarps.

  6. Characterization of functional LB films using electron spin resonance spectroscopy

    International Nuclear Information System (INIS)

    Kuroda, Shin-ichi

    1995-01-01

    The role of ESR spectroscopy in the characterization of functional LB films is discussed. Unpaired electrons in LB films are associated with isolated radical molecules produced by charge transfer, paramagnetic metallic ions such as Cu 2+ , strongly interacting spins in the mixed valence states in charge-transfer salts, and so on. These spins often manifest the functions of materials. They can also act as microscopic probes in the ESR analysis devoted for the elucidation of characteristic properties of LB films. In structural studies, ESR is of particular importance in the analysis of molecular orientation of LB films. ESR can unambiguously determine the orientation of molecules through g-value anisotropy: different g value, different resonance field. Two types of new control methods of molecular orientation in LB films originated from the ESR analysis: study of in-plane orientation in dye LB films which led to the discovery of flow-orientation effect, and observation of drastic change of orientation of Cu-porphyrin in LB films using the trigger molecule, n-hexatriacontane. In the studies of electronic properties, hyperfine interactions between electron and nuclear spins provide information about molecular orbitals and local structures. Stable isotopes have been successfully applied to the stable radicals in merocyanine LB films to identify hyperfine couplings. In conducting LB films composed of charge-transfer salts, quasi-one-dimensional antiferromagnetism in semiconducting films and spin resonance of conduction electrons in metallic films are observed. Results provide microscopic evidence for the development of columnar structures of constituent molecules. Development of new functional LB films may provide more cases where ESR spectroscopy will clarify the nature of such films. (author)

  7. Characterization of Glutaredoxin Fe-S Cluster-Binding Interactions Using Circular Dichroism Spectroscopy.

    Science.gov (United States)

    Albetel, Angela-Nadia; Outten, Caryn E

    2018-01-01

    Monothiol glutaredoxins (Grxs) with a conserved Cys-Gly-Phe-Ser (CGFS) active site are iron-sulfur (Fe-S) cluster-binding proteins that interact with a variety of partner proteins and perform crucial roles in iron metabolism including Fe-S cluster transfer, Fe-S cluster repair, and iron signaling. Various analytical and spectroscopic methods are currently being used to monitor and characterize glutaredoxin Fe-S cluster-dependent interactions at the molecular level. The electronic, magnetic, and vibrational properties of the protein-bound Fe-S cluster provide a convenient handle to probe the structure, function, and coordination chemistry of Grx complexes. However, some limitations arise from sample preparation requirements, complexity of individual techniques, or the necessity for combining multiple methods in order to achieve a complete investigation. In this chapter, we focus on the use of UV-visible circular dichroism spectroscopy as a fast and simple initial approach for investigating glutaredoxin Fe-S cluster-dependent interactions. © 2018 Elsevier Inc. All rights reserved.

  8. Early prediction of water-holding capacity in meat by multivariate vibrational spectroscopy

    DEFF Research Database (Denmark)

    Pedersen, D.K.; Morel, S.; Engelsen, S.B.

    2003-01-01

    about the water-holding capacity (WHC) of the meat. Preliminary studies performed at a research slaughterhouse revealed a high correlation between WHC and both IR (r=0.89) and Raman spectra using Partial Least Squares Regressions (PLSR). The good results were confirmed under industrial conditions using...... FT-IR at-line spectroscopy. However, the latter experiment yielded a somewhat lower correlation (r=0.79). This result is, however, promising for the purpose of finding a method for classification of carcasses with regard to WHC at the slaughter line. The IR region 1800–900 cm−1 contains the best...

  9. Communication: Quantitative multi-site frequency maps for amide I vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Reppert, Mike [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States); Tokmakoff, Andrei, E-mail: tokmakoff@uchicago.edu [Department of Chemistry, University of Chicago, Chicago, Illinois 60637 (United States)

    2015-08-14

    An accurate method for predicting the amide I vibrational spectrum of a given protein structure has been sought for many years. Significant progress has been made recently by sampling structures from molecular dynamics simulations and mapping local electrostatic variables onto the frequencies of individual amide bonds. Agreement with experiment, however, has remained largely qualitative. Previously, we used dipeptide fragments and isotope-labeled constructs of the protein G mimic NuG2b as experimental standards for developing and testing amide I frequency maps. Here, we combine these datasets to test different frequency-map models and develop a novel method to produce an optimized four-site potential (4P) map based on the CHARMM27 force field. Together with a charge correction for glycine residues, the optimized map accurately describes both experimental datasets, with average frequency errors of 2–3 cm{sup −1}. This 4P map is shown to be convertible to a three-site field map which provides equivalent performance, highlighting the viability of both field- and potential-based maps for amide I spectral modeling. The use of multiple sampling points for local electrostatics is found to be essential for accurate map performance.

  10. Statistical strategies to reveal potential vibrational markers for in vivo analysis by confocal Raman spectroscopy

    Science.gov (United States)

    Oliveira Mendes, Thiago de; Pinto, Liliane Pereira; Santos, Laurita dos; Tippavajhala, Vamshi Krishna; Téllez Soto, Claudio Alberto; Martin, Airton Abrahão

    2016-07-01

    The analysis of biological systems by spectroscopic techniques involves the evaluation of hundreds to thousands of variables. Hence, different statistical approaches are used to elucidate regions that discriminate classes of samples and to propose new vibrational markers for explaining various phenomena like disease monitoring, mechanisms of action of drugs, food, and so on. However, the technical statistics are not always widely discussed in applied sciences. In this context, this work presents a detailed discussion including the various steps necessary for proper statistical analysis. It includes univariate parametric and nonparametric tests, as well as multivariate unsupervised and supervised approaches. The main objective of this study is to promote proper understanding of the application of various statistical tools in these spectroscopic methods used for the analysis of biological samples. The discussion of these methods is performed on a set of in vivo confocal Raman spectra of human skin analysis that aims to identify skin aging markers. In the Appendix, a complete routine of data analysis is executed in a free software that can be used by the scientific community involved in these studies.

  11. Vibrational characterization of hexagonal duct core assemblies under various support conditions

    International Nuclear Information System (INIS)

    Bartholf, L.W.; Julyk, L.J.; Ryan, J.A.

    1989-03-01

    Analysis of the dynamic response of advanced Liquid Metal Reactor (LMR) core internals to seismic excitation requires a significant number of simplifying assumptions and idealizations to economically meet the constraints of present-day computer limitations. Fluid coupling and nonlinearities associated with inter-assembly lateral support stiffness and clearances of a large cluster of core internal assemblies are some of the factors that complicate the analytical procedure (Moran, 1976). Well defined test data were needed to quantify these and other uncertainties associated with the use of analytical or numerical computer codes used in the seismic design and analysis of reactor cores. The purpose of the present experimental program was to supplement existing data, such as reported in (Sasaki and Muto, 1983), by developing vibrational characteristics of core assemblies over a range of parameters relative to LMR conceptual designs. The parameters selected for this program were variations in number and location of restraints, restraint-pad to duct-load-pad clearances, and input forcing frequency and g-level. Feature tests were conducted to characterize load pad stiffness and coefficient of restitution, and to calibrate load pads to measure inter-assembly across-flat impact loads. Simulated full-size LMR hexagonal duct core assemblies were used in vibration tests. A single assembly and a row of five assemblies were tested in air to establish modal characteristics and forced response behavior. 2 refs., 7 figs., 1 tab

  12. Characterization of cinematographic films by Laser Induced Breakdown Spectroscopy

    International Nuclear Information System (INIS)

    Gaspard, S.; Oujja, M.; Rebollar, E.; Abrusci, C.; Catalina, F.; Castillejo, M.

    2007-01-01

    The emulsion-coated transparent plastic-base film has been the main carrier for production and preservation of motion picture contents since the 19th century. The knowledge of the composition of black and white silver gelatine cinematographic films is of great importance for the characterization of the photographic process and for identifying the optimum conditions for conservation. A cinematographic film is a multi-component system that consists of a layer of photographic emulsion overcoating a polymeric support (plasticized cellulose triacetate) and a protective transparent cross-linked gelatine layer coating the emulsion. In the present work, Laser Induced Breakdown Spectroscopy (LIBS) is used to characterize the composition of the materials of cinematographic films. LIB spectra of film samples and of different individual film components, polymeric support and reference gelatines, were acquired in vacuum by excitation at 266 nm (Q-switched Nd:YAG laser, 6 ns, 10 Hz). In the cinematographic film, silver lines from the light-sensitive silver halide salts of the photographic emulsion are accompanied by iron, lead, chrome and phosphorus lines. Iron and lead are constituents of film developers, chrome is included in the composition of the hardening agents and phosphorus has its origin in the plasticizer used in the polymeric support. By applying successive pulses on the same spot of the film sample, it was possible to observe through stratigraphic analysis the different layers composition. Additionally, the results obtained reveal the analytical capacity of LIBS for the study and classification of the different gelatine types and qualities used for the protecting layer and the photographic emulsion

  13. Applicability of FTIR-spectroscopy for characterizing waste organic matter

    International Nuclear Information System (INIS)

    Smidt, E.

    2001-12-01

    State and development of waste organic matter were characterized by means of FTIR-spectroscopy. Due to the interaction of infrared light with matter energy is absorbed by chemical functional groups. Chemical preparation steps are not necessary and therefore this method offers a more holistic information about the material. The first part of experiments was focussed on spectra of different waste materials representing various stages of decomposition. Due to characteristics in the fingerprint- region the identity of wastes is provable. Heights of significant bands in the spectrum were measured and relative absorbances were calculated. Changes of relative absorbances indicate the development of organic matter during decomposition. Organic matter of waste samples was compared to organic matter originating from natural analogous processes (peat, soil). The second part of experiments concentrated on a composting process for a period of 260 days. Spectral characteristics of the samples were compared to their chemical, physical and biological data. The change of relative absorbances was reflected by conventional parameters. According to the development of the entire sample humic acids underwent a change as well. For practical use the method offers several possibilities: monitoring of a process, comparison of different processes, quality control of products originating from waste materials and the proof of their identity. (author)

  14. Characterization of different cassava samples by nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Iulianelli, Gisele C.V.; Tavares, Maria I.B.

    2011-01-01

    Cassava root (Manihot esculenta Crantz) is grown in all Brazilian states, being an important product in the diet of Brazilians. For many families of the North and Northeast states, it may represent the main energy source. The cassava root flour has high levels of starch, in addition to containing fiber, lipids and some minerals. There is, however, great genetic variability, which results in differentiation in its chemical composition and structural aspect. Motivated by the economic, nutritional and pharmacological importance of this product, this work is aimed at characterizing six cassava flour samples by NMR spectroscopy. The spectra revealed the main chemical groups. Furthermore, the results confirmed differences on chemical and structural aspect of the samples. For instance, the F1 sample is richer in carbohydrates, while the F4 sample has higher proportion of glycolipids, the F2 sample has higher amylose content and the F6 sample exhibits a greater diversity of glycolipid types. Regarding the molecular structure, the NMR spectra indicated that the F1 sample is more organized at the molecular level, while the F3 and F5 samples are similar in amorphicity and in the molecular packing. (author)

  15. BATMAN beam properties characterization by the beam emission spectroscopy diagnostic

    Science.gov (United States)

    Bonomo, F.; Ruf, B.; Barbisan, M.; Cristofaro, S.; Schiesko, L.; Fantz, U.; Franzen, P.; Pasqualotto, R.; Riedl, R.; Serianni, G.; Wünderlich, D.

    2015-04-01

    The ITER neutral beam heating systems are based on the production and acceleration of negative ions (H/D) up to 1 MV. The requirements for the beam properties are strict: a low core beam divergence (BATMAN (BAvarian Test MAchine for Negative ions) allows for deepening the knowledge of the determination of the beam properties. One of the diagnostics routinely used to this purpose is the Beam Emission Spectroscopy (BES): the Hα light emitted in the beam is detected and the corresponding spectra are evaluated to estimate the beam divergence and the stripping losses. The BES number of lines of sight in BATMAN has been recently increased: five horizontal lines of sight providing a vertical profile of the beam permit to characterize the negative ion beam properties in relation to the source parameters. Different methods of Hα spectra analysis are here taken into account and compared for the estimation of the beam divergence and the amount of stripping. In particular, to thoroughly study the effect of the space charge compensation on the beam divergence, an additional hydrogen injection line has been added in the tank, which allows for setting different background pressure values (one order of magnitude, from about 0.04 Pa up to the source pressure) in the beam drift region.

  16. Spectroscopy characterization and quantum yield determination of quantum dots

    International Nuclear Information System (INIS)

    Ortiz, S N Contreras; Ospino, E Mejía; Cabanzo, R

    2016-01-01

    In this paper we show the characterization of two kinds of quantum dots: hydrophilic and hydrophobic, with core and core/shell respectively, using spectroscopy techniques such as UV-Vis, fluorescence and Raman. We determined the quantum yield in the quantum dots using the quinine sulphate as standard. This salt is commonly used because of its quantum yield (56%) and stability. For the CdTe excitation, we used a wavelength of 549nm and for the CdSe/ZnS excitation a wavelength of 527nm. The results show that CdSe/ZnS (49%) has better fluorescence, better quantum dots, and confirm the fluorescence result. The quantum dots have shown a good fluorescence performance, so this property will be used to replace dyes, with the advantage that quantum dots are less toxic than some dyes like the rhodamine. In addition, in this work we show different techniques to find the quantum dots emission: fluorescence spectrum, synchronous spectrum and Raman spectrum. (paper)

  17. Characterization of Zircaloy-4 oxide layers by impedance spectroscopy

    International Nuclear Information System (INIS)

    Barberis, P.

    1999-01-01

    Two Zircaloy-4 type alloys with different tin contents (0.5 and 1.2 wt%) have been oxidized in autoclave (400 C in steam) for several durations (1-140 days). The film has been characterized by electrochemical impedance spectroscopy (EIS). Several soaking times have been investigated (up to 40 days). The Cole-Cole representation has been used to display and study the data. A simple electrical model has been derived from the observed spectra: the electrical circuit includes two RC loops in series, whose capacitances are frequency dispersed. It is thoroughly related to the layer structure. It has been shown that even before the kinetic transition, the film is constituted of three parts: an inner layer which is compact, an outer layer subdivided in an external region immediately soaked by the electrolyte, and an internal one in which electrolyte diffusion processes can take place. The kinetic transition is interpreted in terms of an abrupt 'compacity' change, both layers degrading at this point. The alloy with high tin content exhibits higher dispersive properties of the oxide layer formed on it, in correlation with its faster oxidation kinetics. (orig.)

  18. Application of FTIR spectroscopy to the characterization of archeological wood.

    Science.gov (United States)

    Traoré, Mohamed; Kaal, Joeri; Martínez Cortizas, Antonio

    2016-01-15

    Two archeological wood samples were studied by attenuated total reflectance Fourier transform infrared (FTIR-ATR) spectroscopy. They originate from a shipwreck in Ribadeo Bay in the northwest of Spain and from a beam wood of an old nave of the Cathedral of Segovia in the central Spain. Principal component analysis was applied to the transposed data matrix (samples as columns and spectral bands as rows) of 43 recorded spectra (18 in the shipwreck and 25 in the beam wood). The results showed differences between the two samples, with a larger proportion of carbohydrates and smaller proportion of lignin in the beam than in the shipwreck wood. Within the beam wood, lignin content was significantly lower in the recent than the old tree rings (P=0.005). These variations can be attributed to species differences between the two woods (oak and pine respectively), with a mixture of guaiacyl and syringyl in hardwood lignin, whereas softwood lignin consists almost exclusively of guaiacyl moieties. The influence of environmental conditions on the FTIR fingerprint was probably reflected by enhanced oxidation of lignin in aerated conditions (beam wood) and hydrolysis of carbohydrates in submerged-anoxic conditions (shipwreck wood). Molecular characterization by analytical pyrolysis of selected samples from each wood type confirmed the interpretation of the mechanisms behind the variability in wood composition obtained by the FTIR-ATR. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. High resolution spectroscopy on adsorbed molecules on a Ni (110)-surface: vibrational states and electronic levels

    International Nuclear Information System (INIS)

    Kardinal, I.

    1998-01-01

    The complementary techniques of HR-XPS and HREELS have been applied to two distinct problems. The first studies adsorption and dissociation of C 2 N 2 on Ni (110) at room temperature (RT) and at 90 K and its co-adsorption with CO. At RT C 2 N 2 dissociates and forms a c(2x2)-CN structure. The resulting CN is found to be bound in the grooves of the (110) surface yielding the lowest C-N vibrational energy yet observed. C 2 N 2 was found to dissociate even at 90 K however the resulting CN overlayer after warming to RT showed remarkable differences to that of the RT adsorption. As well as the in-groove species a number of adsorption sites on the ridges with a bond order higher have been identified. Preadsorbed CO is completely driven of the Ni (110) surface by co-adsorption of CN at RT. HREELS indicates that first CO is desorbed from the on-top-sites and then from the bridge-sites of the (110)-ridges involving a considerable increase of the HREELS cross section for the CO on the bridge-sites. Also the signal intensity of the coadsorbed CN is suppressed by the CO present on the surface. The second study investigated the adsorption of bithiophene (BiT) on clean Ni (110) and the S-modified c(2x2)-S-Ni (110) and p(4x1)-S-Ni (110). The latter provided a strongly structured substrate which forced the assembly of the adsorbed BiT-molecules. The high degree of order of this adsorbate/substrate system was obvious in both the HR-XPS results and the BREELS results with strong azimuthal anisotropy. This system was used to asses the ability to use the HREELS impact selection rules to determine molecular orientation of a reasonably complex adsorbate overlayer. (author)

  20. A variable-temperature scanning tunneling microscope capable of single-molecule vibrational spectroscopy

    International Nuclear Information System (INIS)

    Stipe, B.C.; Rezaei, M.A.; Ho, W.

    1999-01-01

    The design and performance of a variable-temperature scanning tunneling microscope (STM) is presented. The microscope operates from 8 to 350 K in ultrahigh vacuum. The thermally compensated STM is suspended by springs from the cold tip of a continuous flow cryostat and is completely surrounded by two radiation shields. The design allows for in situ dosing and irradiation of the sample as well as for the exchange of samples and STM tips. With the STM feedback loop off, the drift of the tip-sample spacing is approximately 0.001 Angstrom/min at 8 K. It is demonstrated that the STM is well-suited for the study of atomic-scale chemistry over a wide temperature range, for atomic-scale manipulation, and for single-molecule inelastic electron tunneling spectroscopy (IETS). copyright 1999 American Institute of Physics

  1. Rapid identification of closely related muscle foods by vibrational spectroscopy and machine learning.

    Science.gov (United States)

    Ellis, David I; Broadhurst, David; Clarke, Sarah J; Goodacre, Royston

    2005-12-01

    Muscle foods are an integral part of the human diet and during the last few decades consumption of poultry products in particular has increased significantly. It is important for consumers, retailers and food regulatory bodies that these products are of a consistently high quality, authentic, and have not been subjected to adulteration by any lower-grade material either by accident or for economic gain. A variety of methods have been developed for the identification and authentication of muscle foods. However, none of these are rapid or non-invasive, all are time-consuming and difficulties have been encountered in discriminating between the commercially important avian species. Whilst previous attempts have been made to discriminate between muscle foods using infrared spectroscopy, these have had limited success, in particular regarding the closely related poultry species, chicken and turkey. Moreover, this study includes novel data since no attempts have been made to discriminate between both the species and the distinct muscle groups within these species, and this is the first application of Raman spectroscopy to the study of muscle foods. Samples of pre-packed meat and poultry were acquired and FT-IR and Raman measurements taken directly from the meat surface. Qualitative interpretation of FT-IR and Raman spectra at the species and muscle group levels were possible using discriminant function analysis. Genetic algorithms were used to elucidate meaningful interpretation of FT-IR results in (bio)chemical terms and we show that specific wavenumbers, and therefore chemical species, were discriminatory for each type (species and muscle) of poultry sample. We believe that this approach would aid food regulatory bodies in the rapid identification of meat and poultry products and shows particular potential for rapid assessment of food adulteration.

  2. Theory of sum-frequency generation spectroscopy of adsorbed molecules using the density matrix method-broadband vibrational sum-frequency generation and applications

    International Nuclear Information System (INIS)

    Bonn, M; Ueba, H; Wolf, M

    2005-01-01

    A generalized theory of frequency- and time-resolved vibrational sum-frequency generation (SFG) spectroscopy of adsorbates at surfaces is presented using the density matrix formalism. Our theoretical treatment is specifically aimed at addressing issues that accompany the relatively novel SFG approach using broadband infrared pulses. The ultrashort duration of these pulses makes them ideally suited for time-resolved investigations, for which we present a complete theoretical treatment. A second key characteristic of these pulses is their large bandwidth and high intensity, which allow for highly non-linear effects, including vibrational ladder climbing of surface vibrations. We derive general expressions relating the density matrix to SFG spectra, and apply these expressions to specific experimental results by solving the coupled optical Bloch equations of the density matrix elements. Thus, we can theoretically reproduce recent experimentally demonstrated hot band SFG spectra using femtosecond broadband infrared excitation of carbon monoxide (CO) on a Ru(001) surface

  3. Use of vibrational spectroscopy to study protein and DNA structure, hydration, and binding of biomolecules: A combined theoretical and experimental approach

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Jürgensen, Vibeke Würtz; Claussen, Anetta

    2006-01-01

    and experimental approach. The systems we have studied systematically are the amino acids (L-alanine, L-tryptophan, and L-histidine), peptides (N-acetyl L-alanine N'-methyl amide, N-acetyl L-tryptophan N'-methyl amide, N-acetyl L-histidine N'-methyl amide, L-alanyl L-alanine, tri-L-serine, N-acetyl L-alanine L......+disp, RHF, MP2, and DFT methodologies for the modeling studies with the goal of interpreting the experimentally measured vibrational spectra for these molecules to the greatest extent possible and to use this combined approach to understand the structure, function, and electronic properties......We report on our work with vibrational absorption, vibrational circular dichroism, Raman scattering, Raman optical activity, and surface-enhanced Raman spectroscopy to study protein and DNA structure, hydration, and the binding of ligands, drugs, pesticides, or herbicides via a combined theoretical...

  4. Vibrational properties of epitaxial Bi{sub 4}Te{sub 3} films as studied by Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Hao; Pan, Wenwu; Chen, Qimiao; Wu, Xiaoyan [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 865 Changning Road, Shanghai 200050 (China); University of Chinese Academy of Sciences, No.19A Yuquan Road, Beijing 100049 (China); Song, Yuxin, E-mail: songyuxin@mail.sim.ac.cn, E-mail: shumin@chalmers.se; Gong, Qian [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 865 Changning Road, Shanghai 200050 (China); Lu, Pengfei [State Key Laboratory of Information Photonics and Optical Communications, Ministry of Education, Beijing University of Posts and Telecommunications, P.O. Box 72, Beijing 100876 (China); Wang, Shumin, E-mail: songyuxin@mail.sim.ac.cn, E-mail: shumin@chalmers.se [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 865 Changning Road, Shanghai 200050 (China); Department of Microtechnology and Nanoscience, Chalmers University of Technology, 41296 Gothenburg (Sweden)

    2015-08-15

    Bi{sub 4}Te{sub 3}, as one of the phases of the binary Bi–Te system, shares many similarities with Bi{sub 2}Te{sub 3}, which is known as a topological insulator and thermoelectric material. We report the micro-Raman spectroscopy study of 50 nm Bi{sub 4}Te{sub 3} films on Si substrates prepared by molecular beam epitaxy. Raman spectra of Bi{sub 4}Te{sub 3} films completely resolve the six predicted Raman-active phonon modes for the first time. Structural features and Raman tensors of Bi{sub 4}Te{sub 3} films are introduced. According to the wavenumbers and assignments of the six eigenpeaks in the Raman spectra of Bi{sub 4}Te{sub 3} films, it is found that the Raman-active phonon oscillations in Bi{sub 4}Te{sub 3} films exhibit the vibrational properties of those in both Bi and Bi{sub 2}Te{sub 3} films.

  5. Decoding Nucleation and Growth of Zeolitic Imidazolate Framework Thin Films with Atomic Force Microscopy and Vibrational Spectroscopy.

    Science.gov (United States)

    Öztürk, Zafer; Filez, Matthias; Weckhuysen, Bert M

    2017-08-10

    The synthesis of metal-organic framework (MOF) thin films has garnered significant attention during the past decade. By better understanding the parameters governing the nucleation and growth of such thin films, their properties can be rationally tuned, empowering their application as (reactive) membranes. Here, a combined AFM-vibrational spectroscopy research strategy is employed to detail the chemistries governing the nucleation and growth of zeolitic imidazolate framework (ZIF) thin films, in particular isostructural Co-ZIF-67 and Zn-ZIF-8. First, a single step direct synthesis approach is used to investigate the influence of different synthesis parameters -metal/linker ratio, temperature, and metal type- on the thin film nucleation and growth behaviour. While the metal/linker ratio has a pronounced effect on the thin film nucleation rate, the temperature mainly influences the growth kinetics of nuclei forming the thin film. In addition, the nucleation and growth of ZIF thin films is shown to be highly dependent on the electronegativity of the metal type. Thin-film thickness control can be achieved by using a multistep synthesis strategy, implying repetitive applications of single step deposition under identical synthesis conditions, for which a growth mechanism is proposed. This study provides insight into the influence of synthesis parameters on the ZIF thin film properties, using tools at hand to rationally tune MOF thin film properties. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. Rapid vibrational and rotational energy-transfer rates in heated carbon dioxide collisions by double-resonance laser spectroscopy

    International Nuclear Information System (INIS)

    Thomason, M.D.

    1982-07-01

    Rates for resonant vibrational and rotational energy transfer from the 001 state by CO 2 + CO 2 collisions have been measured. All data were obtained by double resonance spectroscopy with CO 2 lasers in a 2.5 meter absorption cell at 700 0 K. Results for rotation transfer include pumped-level relaxation and the response of other 001 levels with ΔJ up to 18. These data are compared to four relevant collision models via a 35-level rate equation analysis. Sequence-band (002 → 101) and hot-band (011 → 110) lasting have been used to observe resonant nu 3 -transfer relaxation involving 001 + 001 reversible 002 + 000, 001 + 100 reversible 101 + 000, and 001 + 010 reversible 011 + 000. A multilevel rate analysis has been utilized to determine the rate coefficients for 001 going to the 002, the 101, and the 011 levels. Part of the hot-band data has been interpreted as due to 110 + 000 reversible 100 + 010, and the associated rate constant has been estimated. The results of the study are compared to the theory and to other experiments

  7. Gold cluster carbonyls: saturated adsorption of CO on gold cluster cations, vibrational spectroscopy, and implications for their structures.

    Science.gov (United States)

    Fielicke, André; von Helden, Gert; Meijer, Gerard; Pedersen, David B; Simard, Benoit; Rayner, David M

    2005-06-15

    We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au(n)(+) clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au(n)(+). Our findings are in agreement with the planar structures of the Au(n)(+) cluster cations with n < or = 7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au(n)(CO)(m)(+) complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au(n)(CO)(m)(+) complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au(n)(+), provide information on the structure of the Au(n)(+)-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.

  8. Cooperative Effects of Zwitterionic-Ionic Surfactant Mixtures on the Interfacial Water Structure Revealed by Sum Frequency Generation Vibrational Spectroscopy.

    Science.gov (United States)

    Pan, Xuecong; Yang, Fangyuan; Chen, Shunli; Zhu, Xuefeng; Wang, Chuanyi

    2018-05-08

    Cooperative effects of a series of equimolar binary zwitterionic-ionic surfactant mixtures on the interfacial water structure at the air-water interfaces have been studied by sum frequency generation vibrational spectroscopy (SFG-VS). For zwitterionic surfactant palmityl sulfobetaine (SNC 16 ), anionic surfactant sodium hexadecyl sulfate (SHS), and cationic surfactant cetyltrimethylammonium bromide (CTAB) with the same length of alkyl chain, significantly enhanced ordering of interfacial water molecules was observed for the zwitterionic-anionic surfactant mixtures SNC 16 -SHS, indicating that SNC 16 interacts more strongly with SHS than with CTAB because of the strong headgroup-headgroup electrostatic attraction for SNC 16 -SHS. Meanwhile, the SFG amplitude ratio of methyl and methylene symmetric stretching modes was used to verify the stronger interaction between SNC 16 and SHS. The conformational order indicator increased from 0.64 for SNC 16 to 7.17 for SNC 16 -SHS but only 0.94 for SNC 16 -CTAB. In addition, another anionic surfactant sodium dodecyl sulfate (SDS) was introduced to study the influence of chain-chain interaction. Decreased SFG amplitude of interfacial water molecules for SNC 16 -SDS was observed. Therefore, both the headgroup-headgroup electrostatic interaction and chain-chain van der Waals attractive interaction of the surfactants play an important role in enhancing the ordering of interfacial water molecules. The results provided experimental and theoretical bases for practical applications of the surfactants.

  9. Site-Specific Measurement of Water Dynamics in the Substrate Pocket of Ketosteroid Isomerase Using Time-Resolved Vibrational Spectroscopy

    Science.gov (United States)

    Jha, Santosh Kumar; Ji, Minbiao; Gaffney, Kelly J.; Boxer, Steven G.

    2012-01-01

    Little is known about the reorganization capacity of water molecules at the active sites of enzymes and how this couples to the catalytic reaction. Here, we study the dynamics of water molecules at the active site of a highly proficient enzyme, Δ5-3-ketosteroid isomerase (KSI), during a light-activated mimic of its catalytic cycle. Photo-excitation of a nitrile containing photo-acid, coumarin183 (C183), mimics the change in charge density that occurs at the active site of KSI during the first step of the catalytic reaction. The nitrile of C183 is exposed to water when bound to the KSI active site, and we used time-resolved vibrational spectroscopy as a site-specific probe to study the solvation dynamics of water molecules in the vicinity of the nitrile. We observed that water molecules at the active site of KSI are highly rigid, during the light-activated catalytic cycle, compared to the solvation dynamics observed in bulk water. Based upon this result we hypothesize that rigid water dipoles at the active site might help in the maintenance of the pre-organized electrostatic environment required for efficient catalysis. The results also demonstrate the utility of nitrile probes in measuring the dynamics of local (H-bonded) water molecules in contrast to the commonly used fluorescence methods which measure the average behavior of primary and subsequent spheres of solvation. PMID:22931297

  10. Electron beam exposure mechanisms in hydrogen silsesquioxane investigated by vibrational spectroscopy and in-situ electron beam induced desorption

    Energy Technology Data Exchange (ETDEWEB)

    Olynick, D.L.; Cord, B.; Schipotinin, A.; Ogletree, D.F.; Schuck, P.J.

    2009-11-13

    Hydrogen Silsesquioxane (HSQ) is used as a high-resolution resist with resolution down below 10nm half-pitch. This material or materials with related functionalities could have widespread impact in nanolithography and nanoscience applications if the exposure mechanism was understood and instabilities controlled. Here we have directly investigated the exposure mechanism using vibrational spectroscopy (both Raman and Fourier transform Infrared) and electron beam desorption spectrocscopy (EBDS). In the non-networked HSQ system, silicon atoms sit at the corners of a cubic structure. Each silicon is bonded to a hydrogen atom and bridges 3 oxygen atoms (formula: HSiO3/2). For the first time, we have shown, via changes in the Si-H2 peak at ~;;2200 cm -1 in the Raman spectra and the release of SiHx products in EBID, that electron-bam exposed materials crosslinks via a redistribution reaction. In addition, we observe the release of significantly more H2 than SiH2 during EBID, which is indicative of additional reaction mechanisms. Additionally, we compare the behavior of HSQ in response to both thermal and electron-beam induced reactions.

  11. Localized vibrations in superconducting YB a2C u3O7 revealed by ultrafast optical coherent spectroscopy

    Science.gov (United States)

    Novelli, Fabio; Giovannetti, Gianluca; Avella, Adolfo; Cilento, Federico; Patthey, Luc; Radovic, Milan; Capone, Massimo; Parmigiani, Fulvio; Fausti, Daniele

    2017-05-01

    The interaction between phonons and high-energy excitations of electronic origin in cuprates and their role in the superconducting mechanisms is still controversial. Here we use coherent vibrational time-domain spectroscopy together with density functional and dynamical mean-field theory calculations to establish a direct link between the c -axis phonon modes and the in-plane electronic charge excitations in optimally doped YB a2C u3O7 . The nonequilibrium Raman tensor is measured by means of the broadband "coherent-phonon" response in pump-probe experiments and is qualitatively described by our model using density functional theory in the frozen-phonon approximation plus single-band dynamical mean-field theory to account for the electronic correlations. The major outcome of our experimental and theoretical study is to establish the link between out-of-plane copper ion displacements and the in-plane electronic correlations, and to estimate at a few unit cells the correlation length of the associated phonon mode. The approach introduced here could help in revealing the complex interplay between fluctuations of different nature and spatial correlation in several strongly correlated materials.

  12. Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy.

    Science.gov (United States)

    Yang, Deheng; Li, Yadong; Liu, Xinyi; Cao, Yue; Gao, Yi; Shen, Y Ron; Liu, Wei-Tao

    2018-04-24

    The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼-20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼-5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.

  13. Alteration of biomacromolecule in corn by steam flaking in relation to biodegradation kinetics in ruminant, revealed with vibrational molecular spectroscopy.

    Science.gov (United States)

    Xu, Ningning; Liu, Jianxin; Yu, Peiqiang

    2018-02-15

    Large scale of steam flaked corn has been used in dairy ration to maintain high milk production level. This study aimed to determine effects of steam flaking on processing-induced intrinsic molecular structure changes that were associated with rumen degradation kinetics and nutrients supply. The advanced vibrational molecular spectroscopy was applied to reveal the processing-induced intrinsic structure changes on a molecular basis. The rumen degradation kinetics and nutrient supply were determined using in situ approach in ruminant livestock system. Raw corn grain (RC) and steam flaked corn grain (SFC) were obtained from two different processing plants. The results showed that (1) Compared to RC, SFC had greater truly digestible non-fiber carbohydrate [tdNFC: 86.8 versus 78.0% dry matter (DM)], but lower truly digestible crude protein [tdCP: 7.7 versus 9.0% DM]. (2) The steam flaking increased (PMolecular absorbance intensities of most carbohydrate biopolymers were greater in SFC (Pmolecular spectral intensities were lower (Pmolecular structure and nutrient interactive study showed that carbohydrate spectral intensities were positively (Pmolecular structure changes had an interactive relationship with rumen degradation kinetics. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

    International Nuclear Information System (INIS)

    McCrea, Keith R.

    2001-01-01

    In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

  15. Characterizing millisecond intermediates in hemoproteins using rapid-freeze-quench resonance Raman spectroscopy.

    Science.gov (United States)

    Matsumura, Hirotoshi; Moënne-Loccoz, Pierre

    2014-01-01

    The combination of rapid freeze quenching (RFQ) with resonance Raman (RR) spectroscopy represents a unique tool with which to investigate the nature of short-lived intermediates formed during the enzymatic reactions of metalloproteins. Commercially available equipment allows trapping of intermediates within a millisecond to second time scale for low-temperature RR analysis resulting in the direct detection of metal-ligand vibrations and porphyrin skeletal vibrations in hemoproteins. This chapter briefly discusses RFQ-RR studies carried out previously in our laboratory and presents, as a practical example, protocols for the preparation of RFQ samples of the reaction of metmyoglobin with nitric oxide (NO) under anaerobic conditions. Also described are important controls and practical procedures for the analysis of these samples by low-temperature RR spectroscopy.

  16. Cavity Ring Down and Thermal Lens Techniques Applied to Vibrational Spectroscopy of Gases and Liquids

    Science.gov (United States)

    Nyaupane, Parashu Ram

    Infrared (IR) and near-infrared (NIR) region gas temperature sensors have been used in the past because of its non-intrusive character and fast time response. In this dissertation cavity ring down (CRD) absorption of oxygen around the region 760 nm has been used to measure the temperature of flowing air in an open optical cavity. This sensor could be a convenient method for measuring the temperature at the input (cold air) and output (hot air) after cooling the blades of a gas turbine. The results could contribute to improvements in turbine blade cooling designs. Additionally, it could be helpful for high temperature measurement in harsh conditions like flames, boilers, and industrial pyrolysis ovens as well as remote sensing. We are interested in experiments that simulate the liquid methane and ethane lakes on Titan which is around the temperature of 94 K. Our specific goal is to quantify the solubility of unsaturated hydrocarbons in liquid ethane and methane. However, it is rather complicated to do so because of the low temperatures, low solubility and solvent effects. So, it is wise to do the experiments at higher temperature and test the suitability of the techniques. In these projects, we were trying to explore if our existing laboratory techniques were sensitive enough to obtain the solubility of unsaturated hydrocarbons in liquid ethane. First, we studied the thermal lens spectroscopy (TLS) of the (Deltav = 6) C-H overtone of benzene and naphthalene in hexane and CCl4 at room temperature.

  17. Perspective: Watching low-frequency vibrations of water in biomolecular recognition by THz spectroscopy

    Science.gov (United States)

    Xu, Yao; Havenith, Martina

    2015-11-01

    Terahertz (THz) spectroscopy has turned out to be a powerful tool which is able to shed new light on the role of water in biomolecular processes. The low frequency spectrum of the solvated biomolecule in combination with MD simulations provides deep insights into the collective hydrogen bond dynamics on the sub-ps time scale. The absorption spectrum between 1 THz and 10 THz of solvated biomolecules is sensitive to changes in the fast fluctuations of the water network. Systematic studies on mutants of antifreeze proteins indicate a direct correlation between biological activity and a retardation of the (sub)-ps hydration dynamics at the protein binding site, i.e., a "hydration funnel." Kinetic THz absorption studies probe the temporal changes of THz absorption during a biological process, and give access to the kinetics of the coupled protein-hydration dynamics. When combined with simulations, the observed results can be explained in terms of a two-tier model involving a local binding and a long range influence on the hydration bond dynamics of the water around the binding site that highlights the significance of the changes in the hydration dynamics at recognition site for biomolecular recognition. Water is shown to assist molecular recognition processes.

  18. Sum frequency generation (SFG) vibrational spectroscopy of planar phosphatidylethanolamine hybrid bilayer membranes under water.

    Science.gov (United States)

    Kett, Peter J N; Casford, Michael T L; Davies, Paul B

    2010-06-15

    Sum frequency generation (SFG) spectroscopy has been used to study the structure of phosphatidylethanolamine hybrid bilayer membranes (HBMs) under water at ambient temperatures. The HBMs were formed using a modified Langmuir-Schaefer technique and consisted of a layer of dipalmitoyl phosphatidylethanolamine (DPPE) physisorbed onto an octadecanethiol (ODT) self-assembled monolayer (SAM) at a series of surface pressures from 1 to 40 mN m(-1). The DPPE and ODT were selectively deuterated so that the contributions to the SFG spectra from the two layers could be determined separately. SFG spectra in both the C-H and C-D stretching regions confirmed that a monolayer of DPPE had been adsorbed to the ODT SAM and that there were gauche defects within the alkyl chains of the phospholipid. On adsorption of a layer of DPPE, methylene modes from the ODT SAM were detected, indicating that the phospholipid had partially disordered the alkanethiol monolayer. SFG spectra recorded in air indicated that removal of water from the surface of the HBM resulted in disruption of the DPPE layer and the formation of phospholipid bilayers.

  19. Evidence for Tautomerisation of Glutamine in BLUF Blue Light Receptors by Vibrational Spectroscopy and Computational Chemistry

    Science.gov (United States)

    Domratcheva, Tatiana; Hartmann, Elisabeth; Schlichting, Ilme; Kottke, Tilman

    2016-01-01

    BLUF (blue light sensor using flavin) domains regulate the activity of various enzymatic effector domains in bacteria and euglenids. BLUF features a unique photoactivation through restructuring of the hydrogen-bonding network as opposed to a redox reaction or an isomerization of the chromophore. A conserved glutamine residue close to the flavin chromophore plays a central role in the light response, but the underlying modification is still unclear. We labelled this glutamine with 15N in two representative BLUF domains and performed time-resolved infrared double difference spectroscopy. The assignment of the signals was conducted by extensive quantum chemical calculations on large models with 187 atoms reproducing the UV-vis and infrared signatures of BLUF photoactivation. In the dark state, the comparatively low frequency of 1,667 cm−1 is assigned to the glutamine C=O accepting a hydrogen bond from tyrosine. In the light state, the signature of a tautomerised glutamine was extracted with the C=N stretch at ~1,691 cm−1 exhibiting the characteristic strong downshift by 15N labelling. Moreover, an indirect isotope effect on the flavin C4=O stretch was found. We conclude that photoactivation of the BLUF receptor does not only involve a rearrangement of hydrogen bonds but includes a change in covalent bonds of the protein. PMID:26947391

  20. Application of Vibrational Spectroscopy Supported by Theoretical Calculations in Identification of Amorphous and Crystalline Forms of Cefuroxime Axetil

    Directory of Open Access Journals (Sweden)

    Alicja Talaczyńska

    2015-01-01

    Full Text Available FT-IR and Raman scattering spectra of cefuroxime axetil were proposed for identification studies of its crystalline and amorphous forms. An analysis of experimental spectra was supported by quantum-chemical calculations performed with the use of B3LYP functional and 6-31G(d,p as a basis set. The geometric structure of a cefuroxime axetil molecule, HOMO and LUMO orbitals, and molecular electrostatic potential were also determined by using DFT (density functional theory. The benefits of applying FT-IR and Raman scattering spectroscopy for characterization of drug subjected to degradation were discussed.

  1. Laboratory characterization and astrophysical detection of vibrationally excited states of vinyl cyanide in Orion-KL

    Science.gov (United States)

    López, A.; Tercero, B.; Kisiel, Z.; Daly, A. M.; Bermúdez, C.; Calcutt, H.; Marcelino, N.; Viti, S.; Drouin, B. J.; Medvedev, I. R.; Neese, C. F.; Pszczółkowski, L.; Alonso, J. L.; Cernicharo, J.

    2014-12-01

    Context. We perform a laboratory characterization in the 18-1893 GHz range and astronomical detection between 80-280 GHz in Orion-KL with IRAM-30 m of CH2CHCN (vinyl cyanide) in its ground and vibrationally excited states. Aims: Our aim is to improve the understanding of rotational spectra of vibrationally excited vinyl cyanide with new laboratory data and analysis. The laboratory results allow searching for these excited state transitions in the Orion-KL line survey. Furthermore, rotational lines of CH2CHCN contribute to the understanding of the physical and chemical properties of the cloud. Methods: Laboratory measurements of CH2CHCN made on several different frequency-modulated spectrometers were combined into a single broadband 50-1900 GHz spectrum and its assignment was confirmed by Stark modulation spectra recorded in the 18-40 GHz region and by ab-initio anharmonic force field calculations. For analyzing the emission lines of vinyl cyanide detected in Orion-KL we used the excitation and radiative transfer code (MADEX) at LTE conditions. Results: Detailed characterization of laboratory spectra of CH2CHCN in nine different excited vibrational states: ν11 = 1, ν15 = 1, ν11 = 2, ν10 = 1 ⇔ (ν11 = 1,ν15 = 1), ν11 = 3/ν15 = 2/ν14 = 1, (ν11 = 1,ν10 = 1) ⇔ (ν11 = 2,ν15 = 1), ν9 = 1, (ν11 = 1,ν15 = 2) ⇔ (ν10 = 1,ν15 = 1) ⇔ (ν11 = 1,ν14 = 1), and ν11 = 4 are determined, as well as the detection of transitions in the ν11 = 2 and ν11 = 3 states for the first time in Orion-KL and of those in the ν10 = 1 ⇔ (ν11 = 1,ν15 = 1) dyad of states for the first time in space. The rotational transitions of the ground state of this molecule emerge from four cloud components of hot core nature, which trace the physical and chemical conditions of high mass star forming regions in the Orion-KL Nebula. The lowest energy vibrationally excited states of vinyl cyanide, such as ν11 = 1 (at 328.5 K), ν15 = 1 (at 478.6 K), ν11 = 2 (at 657.8 K), the ν10

  2. From Vibrational Spectroscopy to Force Fields and Structures of Saccharides: New Computational Algorithms and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Pincu, Madeleine [Univ. of California, Irvine, CA (United States); Gerber, Robert Benny [Univ. of California, Irvine, CA (United States). Dept. of Chemistry

    2013-07-17

    vibrational bands involving the shared proton were strongly shifted to lower frequencies ( by about ~ 500 cm-1 for the symmetric mode, in this case). A similar motif was also observed recently by us in protonated cellobiose, indicating that this might be a common mechanism for interaction of a proton with sugars, perhaps similar to the proton wires observed in proteins. The simulations with protonated sugars also shed light on different mechanisms of interaction of a sugar with a proton, including formation of a carboxonium ion, mutarotation events, ring puckering and in the disaccharide cellobiose, the breaking of the glycosidic bond (in both forms of cis and trans). One final highlight to note in this summary, is the finding that in the monosaccharide beta-D-Galactose a hydroxyl ion abstracts a proton (forming water) in a barrierless process at room temperature, but the water remains bound to the sugar backbone, though it migrates around it; actual degradation occurs at ~500 K when water leaves the sugar. However, the study also shows that the water abstraction reaction can be reversed in the presence of 2 additional water molecules complexed with the sugar.

  3. BATMAN beam properties characterization by the beam emission spectroscopy diagnostic

    International Nuclear Information System (INIS)

    Bonomo, F.; Ruf, B.; Schiesko, L.; Fantz, U.; Franzen, P.; Riedl, R.; Wünderlich, D.; Barbisan, M.; Pasqualotto, R.; Serianni, G.; Cristofaro, S.

    2015-01-01

    The ITER neutral beam heating systems are based on the production and acceleration of negative ions (H/D) up to 1 MV. The requirements for the beam properties are strict: a low core beam divergence (< 0.4 °) together with a low source pressure (≤ 0.3 Pa) would permit to reduce the ion losses along the beamline, keeping the stripping particle losses below 30%. However, the attainment of such beam properties is not straightforward. At IPP, the negative ion source testbed BATMAN (BAvarian Test MAchine for Negative ions) allows for deepening the knowledge of the determination of the beam properties. One of the diagnostics routinely used to this purpose is the Beam Emission Spectroscopy (BES): the H α light emitted in the beam is detected and the corresponding spectra are evaluated to estimate the beam divergence and the stripping losses. The BES number of lines of sight in BATMAN has been recently increased: five horizontal lines of sight providing a vertical profile of the beam permit to characterize the negative ion beam properties in relation to the source parameters. Different methods of H α spectra analysis are here taken into account and compared for the estimation of the beam divergence and the amount of stripping. In particular, to thoroughly study the effect of the space charge compensation on the beam divergence, an additional hydrogen injection line has been added in the tank, which allows for setting different background pressure values (one order of magnitude, from about 0.04 Pa up to the source pressure) in the beam drift region

  4. Applications of the Raman spectroscopy in the materials characterization

    International Nuclear Information System (INIS)

    Jimenez S, S.; Escobar A, L.; Camacho L, M. A.

    2011-01-01

    The study field of the science and technology of surfaces and materials have been of primordial importance in the last years due to the impact that they have the knowledge that it generates in diverse areas. For this reason, the Mexican Society of Science and Technology of Surfaces and Materials has focused a good part of their investigation activities toward the materials science and technology development. Inside the investigation fields carried out by members of this Society, are the following: semiconductors, thin films, hard coatings, deposit techniques, plasmas, biomaterials, Ab-initio calculations, characterization techniques, photo-thermal properties, solar cells, nano science, magnetism, superconductivity and related topics. Among the techniques used for this purpose is the Raman Spectroscopy (Rs), which has demonstrated to be a powerful and versatile tool in the materials study. In the last three congresses that the Society has organized, an average of 42 works related with this topic have been presented, what gave the rule to prepare this book whose objective is on one hand diffusing part of the works that carry out different groups integrated with members of the Society that use the Rs like an important tool in its investigation work. A second objective is that it can serve like support to the students that begin to be involved, or that they are already involved, in topics where the Rs can have a decisive paper in the development of its projects. It is also expected that some of the topics included in the book are of utility for professors and researches that already uses the Rs, or that it can be of help for those who are beginning in this technique as alternative or like complementary analysis tool. (Author)

  5. Vibrational spectroscopy and molecular dynamics of water monomers and dimers adsorbed on polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Simon, Aude; Rapacioli, Mathias; Mascetti, Joëlle; Spiegelman, Fernand

    2012-05-21

    This paper reports structures, energetics, dynamics and spectroscopy of H2O and (H2O)2 systems adsorbed on coronene (C24H12), a compact polycyclic aromatic hydrocarbon (PAH). On-the-fly Born-Oppenheimer molecular dynamics simulations are performed for temperatures T varying from 10 to 300 K, on a potential energy surface obtained within the self-consistent-charge density-functional based tight-binding (SCC-DFTB) approach. Anharmonic infrared (IR) spectra are extracted from these simulations. We first benchmark the SCC-DFTB semi-empirical hamiltonian vs. DFT (Density Functional Theory) calculations that include dispersion, on (C6H6)(H2O)1,2 small complexes. We find that charge corrections and inclusion of dispersion contributions in DFTB are necessary to obtain consistent structures, energetics and IR spectra. Using this Hamiltonian, the structures, energetics and IR features of the low-energy isomers of (C24H12)(H2O)1,2 are found to be similar to the DFT ones, with evidence for a stabilizing edge-coordination. The temperature dependence of the motions of H2O and (H2O)2 on the surface of C24H12 is analysed, revealing ultra-fast periodic motion. The water dimer starts diffusing at a higher temperature than the water monomer (150 K vs. 10 K respectively), which appears to be consistent with the binding energies. Qualitative and quantitative analyses of the effects of T on the IR spectra are performed. Anharmonic factors in particular are derived and it is shown that they can be used as signatures for the presence of PAH-water complexes. Finally, this paper lays the foundations for the studies of larger (PAH)m(H2O)n clusters, that can be treated with the efficient computational approach benchmarked in this paper.

  6. Characterisation of the SOFC material, LaCrO 3, using vibrational spectroscopy

    Science.gov (United States)

    Tompsett, G. A.; Sammes, N. M.

    LaCrO 3 is reported to undergo a low to high temperature (HT) phase transition from orthorhombic ( Pnma) to rhombohedral ( R-3 c), at ca. 255 °C. The phases involved in the low temperature phase transition of LaCrO 3 have been determined using Raman spectroscopy at temperatures from -196 to 300 °C. There are nine Raman bands observed from a total of 24 predicted modes, seven of which are assigned from comparison with the Raman profile and relative band positions observed and calculated for the isostructural compound, YMnO 3, as follows: 131(B 2g), 150(B 3g), 174(A g), 252(B 1g), 279(A g), 441(A g) and 590(A g) cm -1. A phase transformation was observed at ca. 260 °C from the change in the Raman profile. The high temperature rhombohedral phase of LaCrO 3 had four bands which are assigned as follows: 58(E g), 161(E g), 288(A 1g) and 434(E g, E g) cm -1, from comparison with the Raman profile and relative band positions observed for the isostructural compound, NdAlO 3. The Fourier transform infrared (FTIR) spectrum of LaCrO 3 showed a total of eight bands discernible at room temperature from 25 predicted modes for the orthorhombic structure. The mode assignments were determined by comparison with the Raman profile and relative band positions observed and calculated for the isostructural compound, SmAlO 3, as follows: 138(B 2u), 166(B 3u), 197(B 1u), 240(B 3u), 266(B 2u), 332(B 2u), 357(B 2u), 381(B 3u), 425(B 3u), 446(B 1u), 471(B 3u), 493(B 3u), 573(B 1u), 606(B 3u) and 670 (B 1u) cm -1.

  7. Sum Frequency Generation Vibrational Spectroscopy of 1,3-Butadiene Hydrogenation on 4 nm Pt@SiO 2 , Pd@SiO 2 , and Rh@SiO 2 Core–Shell Catalysts

    KAUST Repository

    Krier, James M.; Michalak, William D.; Cai, Xiaojun; Carl, Lindsay; Komvopoulos, Kyriakos; Somorjai, Gabor A.

    2015-01-01

    NPs (Stöber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective

  8. Syntheses, crystal structures, NMR spectroscopy, and vibrational spectroscopy of Sr(PO{sub 3}F).H{sub 2}O and Sr(PO{sub 3}F)

    Energy Technology Data Exchange (ETDEWEB)

    Jantz, Stephan G.; Hoeppe, Henning A. [Lehrstuhl fuer Festkoerperchemie, Institut fuer Physik, Universitaet Augsburg (Germany); Wuellen, Leo van; Fischer, Andreas [Lehrstuhl fuer Chemische Physik und Materialwissenschaften, Institut fuer Physik, Universitaet Augsburg (Germany); Libowitzky, Eugen [Institute for Mineralogy and Crystallography, Faculty of Geosciences, Geography and Astronomy, University of Vienna (Austria); Baran, Enrique J. [Centro de Quimica Inorganica (CEQUINOR/CONICET, UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata (Argentina); Weil, Matthias [Institute for Chemical Technologies and Analytics, Division Structural Chemistry, Vienna University of Technology (Austria)

    2016-03-15

    Single crystals of Sr(PO{sub 3}F).H{sub 2}O {P2_1/c, Z = 4, a = 7.4844(2) Aa, b = 7.0793(2) Aa, c = 8.4265(2) Aa, β = 108.696(1) , V = 422.91(2) Aa"3, 2391 F_o"2, 70 parameters, R_1[F"2 > 2σ(F"2)] = 0.036; wR_2(F"2 all) = 0.049, S = 1.054} were grown from an aqueous solution by a metathesis reaction. The structure comprises [SrO{sub 8}] polyhedra and PO{sub 3}F tetrahedra that form a layered arrangement parallel to (100). The topotactic dehydration of this phase proceeds between 80 and 140 C to afford Sr(PO{sub 3}F). The monazite-type crystal structure of Sr(PO{sub 3}F) was elucidated from the X-ray powder data by simulated annealing [P2{sub 1}/c, Z = 4, a = 6.71689(9) Aa, b = 7.11774(11) Aa, c = 8.66997(13) Aa, β = 128.0063(7) , V = 326.605(8) Aa{sup 3}, R{sub p} = 0.010, R{sub wp} = 0.015, R{sub F} = 0.030]. During dehydration, the structure of Sr(PO{sub 3}F) .H{sub 2}O collapses along [100] from a layered arrangement into a framework structure, accompanied by a change of the coordination number of the Sr{sup 2+} ions from eight to nine. The magic-angle spinning (MAS) NMR and vibrational spectroscopy data of both phases are discussed. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Fabrication and characterization of non-resonant magneto-mechanical low-frequency vibration energy harvester

    Science.gov (United States)

    Nammari, Abdullah; Caskey, Logan; Negrete, Johnny; Bardaweel, Hamzeh

    2018-03-01

    This article presents a non-resonant magneto-mechanical vibration energy harvester. When externally excited, the energy harvester converts vibrations into electric charge using a guided levitated magnet oscillating inside a multi-turn coil that is fixed around the exterior of the energy harvester. The levitated magnet is guided using four oblique mechanical springs. A prototype of the energy harvester is fabricated using additive manufacturing. Both experiment and model are used to characterize the static and dynamic behavior of the energy harvester. Measured restoring forces show that the fabricated energy harvester retains a mono-stable potential energy well with desired stiffness nonlinearities. Results show that magnetic spring results in hardening effect which increases the resonant frequency of the energy harvester. Additionally, oblique mechanical springs introduce geometric, negative, nonlinear stiffness which improves the harvester's response towards lower frequency spectrum. The unique design can produce a tunable energy harvester with multi-well potential energy characteristics. A finite element model is developed to estimate the average radial flux density experienced by the multi-turn coil. Also, a lumped parameter model of the energy harvester is developed and validated against measured data. Both upward and downward frequency sweeps are performed to determine the frequency response of the harvester. Results show that at higher excitation levels hardening effects become more apparent, and the system dynamic response turns into non-resonant. Frequency response curves exhibit frequency jump phenomena as a result of coexistence of multiple energy states at the frequency branch. The fabricated energy harvester is hand-held and measures approximately 100.5 [cm3] total volume. For a base excitation of 1.0 g [m/s2], the prototype generates a peak voltage and normalized power density of approximately 3.5 [V] and 0.133 [mW/cm3 g2], respectively, at 15.5 [Hz].

  10. Vibrational dynamics (IR, Raman, NRVS) and DFT study of new antitumor tetranuclearstannoxanecluster, Sn(IV)$-$oxo$-${di$-$o$-$vanillin} dimethyl dichloride

    Energy Technology Data Exchange (ETDEWEB)

    Arjmand, F. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Sharma, S. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Usman, M. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry; Leu, B. M. [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Hu, M. Y. [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Toupet, L. [Univ. de Rennes, Rennes (France). Inst. de Physique de Rennes; Gosztola, David J. [Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Tabassum, S. [Aligarh Muslim Univ., Aligarh (India). Dept. of Chemistry

    2016-06-21

    The vibrational dynamics of a newly synthesized tetrastannoxane was characterized with a combination of experimental (Raman, IR and tin-based nuclear resonance vibrational spectroscopy) and computational (DFT/B3LYP) methods, with an emphasis on the vibrations of the tin sites. The cytotoxic activity revealed a significant regression selectively against the human pancreatic cell lines.

  11. Alteration of biomacromolecule in corn by steam flaking in relation to biodegradation kinetics in ruminant, revealed with vibrational molecular spectroscopy

    Science.gov (United States)

    Xu, Ningning; Liu, Jianxin; Yu, Peiqiang

    2018-02-01

    Large scale of steam flaked corn has been used in dairy ration to maintain high milk production level. This study aimed to determine effects of steam flaking on processing-induced intrinsic molecular structure changes that were associated with rumen degradation kinetics and nutrients supply. The advanced vibrational molecular spectroscopy was applied to reveal the processing-induced intrinsic structure changes on a molecular basis. The rumen degradation kinetics and nutrient supply were determined using in situ approach in ruminant livestock system. Raw corn grain (RC) and steam flaked corn grain (SFC) were obtained from two different processing plants. The results showed that (1) Compared to RC, SFC had greater truly digestible non-fiber carbohydrate [tdNFC: 86.8 versus 78.0% dry matter (DM)], but lower truly digestible crude protein [tdCP: 7.7 versus 9.0% DM]. (2) The steam flaking increased (P < 0.01) rumen degradable DM (RDDM) and starch (RDSt), but decreased (P < 0.01) rumen degradable protein (RDP). (3) Molecular absorbance intensities of most carbohydrate biopolymers were greater in SFC (P < 0.01), but protein amides associated molecular spectral intensities were lower (P < 0.01) in SFC. (4). The molecular structure and nutrient interactive study showed that carbohydrate spectral intensities were positively (P < 0.10) associated with RDDM and RDSt and protein amide spectral intensities were positively (P < 0.10) associated with RDP. This results indicated that the steam flaking induced molecular structure changes had an interactive relationship with rumen degradation kinetics.

  12. Surface and buried interfacial structures of epoxy resins used as underfills studied by sum frequency generation vibrational spectroscopy.

    Science.gov (United States)

    Vázquez, Anne V; Holden, Brad; Kristalyn, Cornelius; Fuller, Mike; Wilkerson, Brett; Chen, Zhan

    2011-05-01

    Flip chip technology has greatly improved the performance of semiconductor devices, but relies heavily on the performance of epoxy underfill adhesives. Because epoxy underfills are cured in situ in flip chip semiconductor devices, understanding their surface and interfacial structures is critical for understanding their adhesion to various substrates. Here, sum frequency generation (SFG) vibrational spectroscopy was used to study surface and buried interfacial structures of two model epoxy resins used as underfills in flip chip devices, bisphenol A digylcidyl ether (BADGE) and 1,4-butanediol diglycidyl ether (BDDGE). The surface structures of these epoxies were compared before and after cure, and the orientations of their surface functional groups were deduced to understand how surface structural changes during cure may affect adhesion properties. Further, the effect of moisture exposure, a known cause of adhesion failure, on surface structures was studied. It was found that the BADGE surface significantly restructured upon moisture exposure while the BDDGE surface did not, showing that BADGE adhesives may be more prone to moisture-induced delamination. Lastly, although surface structure can give some insight into adhesion, buried interfacial structures more directly correspond to adhesion properties of polymers. SFG was used to study buried interfaces between deuterated polystyrene (d-PS) and the epoxies before and after moisture exposure. It was shown that moisture exposure acted to disorder the buried interfaces, most likely due to swelling. These results correlated with lap shear adhesion testing showing a decrease in adhesion strength after moisture exposure. The presented work showed that surface and interfacial structures can be correlated to adhesive strength and may be helpful in understanding and designing optimized epoxy underfill adhesives.

  13. Using polarized Raman spectroscopy and the pseudospectral method to characterize molecular structure and function

    Science.gov (United States)

    Weisman, Andrew L.

    Electronic structure calculation is an essential approach for determining the structure and function of molecules and is therefore of critical interest to physics, chemistry, and materials science. Of the various algorithms for calculating electronic structure, the pseudospectral method is among the fastest. However, the trade-off for its speed is more up-front programming and testing, and as a result, applications using the pseudospectral method currently lag behind those using other methods. In Part I of this dissertation, we first advance the pseudospectral method by optimizing it for an important application, polarized Raman spectroscopy, which is a well-established tool used to characterize molecular properties. This is an application of particular importance because often the easiest and most economical way to obtain the polarized Raman spectrum of a material is to simulate it; thus, utilization of the pseudospectral method for this purpose will accelerate progress in the determination of molecular properties. We demonstrate that our implementation of Raman spectroscopy using the pseudospectral method results in spectra that are just as accurate as those calculated using the traditional analytic method, and in the process, we derive the most comprehensive formulation to date of polarized Raman intensity formulas, applicable to both crystalline and isotropic systems. Next, we apply our implementation to determine the orientations of crystalline oligothiophenes -- a class of materials important in the field of organic electronics -- achieving excellent agreement with experiment and demonstrating the general utility of polarized Raman spectroscopy for the determination of crystal orientation. In addition, we derive from first-principles a method for using polarized Raman spectra to establish unambiguously whether a uniform region of a material is crystalline or isotropic. Finally, we introduce free, open-source software that allows a user to determine any of a

  14. Point defects in gallium arsenide characterized by positron annihilation spectroscopy and deep level transient spectroscopy

    International Nuclear Information System (INIS)

    Mih, R.; Gronsky, R.; Sterne, P.A.

    1995-01-01

    Positron annihilation lifetime spectroscopy (PALS) is a unique technique for detection of vacancy related defects in both as-grown and irradiated materials. The authors present a systematic study of vacancy defects in stoichiometrically controlled p-type Gallium Arsenide grown by the Hot-Wall Czochralski method. Microstructural information based on PALS, was correlated to crystallographic data and electrical measurements. Vacancies were detected and compared to electrical levels detected by deep level transient spectroscopy and stoichiometry based on crystallographic data

  15. Characterization of Paracoccidioides brasiliensis by FT-IR spectroscopy and nanotechnology

    Science.gov (United States)

    Ferreira, Isabelle; Ferreira-Strixino, Juliana; Castilho, Maiara L.; Campos, Claudia B. L.; Tellez, Claudio; Raniero, Leandro

    2016-01-01

    Paracoccidioides brasiliensis, the etiological agent of paracoccidioidomycosis, is a dimorphic fungus existing as mycelia in the environment (or at 25 °C in vitro) and as yeast cells in the human host (or at 37 °C in vitro). Because mycological examination of lesions in patients frequently is unable to show the presence of the fungus and serological tests can misdiagnose the disease with other mycosis, the development of new approach's for molecular identification of P. brasiliensis spurges is needed. This study describes the use of a gold nanoprobe of a known gene sequence of P. brasiliensis as a molecular tool to identify P. brasiliensis by regular polymerase chain reaction (PCR) associated with a colorimetric methods. This approach is suitable for testing in remote areas because it does not require any further step than gene amplification, being safer and cheaper than electrophoresis methods. The proposed test showed a color change of the PCR reaction mixture from red to blue in negative samples, whereas the solution remains red in positive samples. We also performed a Fourier Transform Infrared (FT-IR) Spectroscopy analysis to characterize and compare the chemical composition between yeast and mycelia forms, which revealed biochemical differences between these two forms. The analysis of the spectra showed that differences were distributed in chemical bonds of proteins, lipids and carbohydrates. The most prominent difference between both forms was vibration modes related to 1,3-β-glucan usually found in mycelia and 1,3-α-glucan found in yeasts and also chitin forms. In this work, we introduce FT-IR as a new method suitable to reveal overall differences that biochemically distinguish each form of P. brasiliensis that could be additionally used to discriminate biochemical differences among a single form under distinct environmental conditions.

  16. Synthesis, X-ray crystallography characterization, vibrational spectroscopic, molecular electrostatic potential maps, thermodynamic properties studies of N,N'-di(p-thiazole)formamidine.

    Science.gov (United States)

    Rofouei, M K; Fereyduni, E; Sohrabi, N; Shamsipur, M; Attar Gharamaleki, J; Sundaraganesan, N

    2011-01-01

    In this work, we will report a combined experimental and theoretical study on molecular and vibrational structure of N,N'-di(p-thiazole)formamidine (DpTF). DpTF has been synthesized and characterized by elemental analysis, FT-IR, FT-Raman, 1H NMR, 13C NMR spectroscopy and X-ray single crystal diffraction. The FT-IR and FT-Raman spectra of DpTF were recorded in the solid phase. The optimized geometry was calculated by HF and B3LYP methods using 6-31G(d) basis set. The FT-IR and FT-Raman spectra of DpTF was calculated at the HF/B3LYP/6-31G(d) level and were interpreted in terms of potential energy distribution (PED) analysis. The scaled theoretical wavenumber showed very good agreement with the experimental values. A detailed interpretation of the infrared and Raman spectra of DpTF was reported. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between Cp,m°, Sm°, Hm° and temperatures. Furthermore, molecular electrostatic potential maps (MESP) and total dipole moment properties of the compound have been calculated. Copyright © 2010 Elsevier B.V. All rights reserved.

  17. Synthesis and characterization of aromatic self-assembled monolayers containing methylene and ethyleneglycol entities by means of sum-frequency generation spectroscopy

    International Nuclear Information System (INIS)

    Dreesen, L.; Sartenaer, Y.; Peremans, A.; Thiry, P.A.; Humbert, C.; Grugier, J.; Marchand-Brynaert, J.

    2006-01-01

    We use infrared-visible sum-frequency generation (SFG) spectroscopy in order to investigate the adsorption properties on Pt(111) of molecules having CH 3 -C 6 H 4 -(O-CH 2 -CH 2 ) n -O-(CH 2 ) m -SH as general chemical formula. We synthesized three molecules defined by the values m = 5 n = 4, m = 11 n = 4, m = 11 n = 8 and characterized them by Nuclear Magnetic Resonance spectroscopy. Thanks to spectroscopic measurements, we show that these molecules build self-assembled monolayers on Pt(111). First, the weak SFG signals arising from the ad-layer indicate low order and surface coverage of the substrate by these molecules. Next, the vibrational fingerprints of the aforementioned molecules are determined between 2825 and 3125 cm - 1 and the observed SFG spectral features are ascribed on the basis of the analysis of shorter and simpler molecules (1-dodecanethiol, 4-methylbenzenethiol and CH 3 -C 6 H 4 -O-(CH 2 ) 11 -SH) also adsorbed on Pt(111). The occurrence of methylene vibration modes indicates a significant amount of chain defects whatever the n and m numbers are. Finally, the identification of a particular vibration mode, characteristic of the aromatic ring, enables us to qualitatively discuss the effect of the number of methylene and ethylene glycol entities on its orientation. More precisely, higher these numbers, more tilted (with respect to the substrate normal) the aromatic ring plane is

  18. Application of high-resolution photoelectron spectroscopy: Vibrational resolved C 1s and O 1s spectra of CO adsorbed on Ni(100)

    Energy Technology Data Exchange (ETDEWEB)

    Foehlisch, A.; Nilsson, A.; Martensson, N. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    There are various effects which determine the line shape of a core-level electron spectrum. These are due to the finite life-time of the core hole, inelastic scattering of the outgoing photoelectron, electronic shake-up and shake-off processes and vibrational excitations. For free atoms and molecules the different contributions to the observed line shapes can often be well separated. For solids, surfaces and adsorbates the line shapes are in general much broader and it has in the past been assumed that no separation of the various contributions can be made. In the present report the authors will show that this is indeed not the case. Surprisingly, the vibrational fine structure of CO adsorbed on Ni(100) can be resolved in the C 1s and O 1s electron spectra. This was achieved by the combination of highly monochromatized soft X-rays from B18.0 with a high resolution Scienta 200 mm photoelectron spectrometer. X-ray photoelectron spectroscopy (XPS) with tunable excitation energy yields as a core level spectroscopy atomic and site-specific information. The presented measurements allow for a determination of internuclear distances and potential energy curves in corehole ionized adsorbed molecules. The authors analysis of the c(2x2) phase CO/Ni(100) on {open_quotes}top{close_quotes} yielded a vibrational splitting of 217 +/- 2 meV for C 1s ionization. For O 1s ionization a splitting of 173 +/- 8 meV was found.

  19. Vibration-induced electrical noise in a cryogen-free dilution refrigerator: Characterization, mitigation, and impact on qubit coherence

    Energy Technology Data Exchange (ETDEWEB)

    Kalra, Rachpon; Laucht, Arne; Dehollain, Juan Pablo; Bar, Daniel; Freer, Solomon; Simmons, Stephanie; Muhonen, Juha T.; Morello, Andrea, E-mail: a.morello@unsw.edu.au [Centre for Quantum Computation and Communication Technology, School of Electrical Engineering and Telecommunications, UNSW Australia, Sydney NSW 2052 (Australia)

    2016-07-15

    Cryogen-free low-temperature setups are becoming more prominent in experimental science due to their convenience and reliability, and concern about the increasing scarcity of helium as a natural resource. Despite not having any moving parts at the cold end, pulse tube cryocoolers introduce vibrations that can be detrimental to the experiments. We characterize the coupling of these vibrations to the electrical signal observed on cables installed in a cryogen-free dilution refrigerator. The dominant electrical noise is in the 5–10 kHz range and its magnitude is found to be strongly temperature dependent. We test the performance of different cables designed to diagnose and tackle the noise, and find triboelectrics to be the dominant mechanism coupling the vibrations to the electrical signal. Flattening a semi-rigid cable or jacketing a flexible cable in order to restrict movement within the cable, successfully reduces the noise level by over an order of magnitude. Furthermore, we characterize the effect of the pulse tube vibrations on an electron spin qubit device in this setup. Coherence measurements are used to map out the spectrum of the noise experienced by the qubit, revealing spectral components matching the spectral signature of the pulse tube.

  20. An intelligent sensor array distributed system for vibration analysis and acoustic noise characterization of a linear switched reluctance actuator.

    Science.gov (United States)

    Salvado, José; Espírito-Santo, António; Calado, Maria

    2012-01-01

    This paper proposes a distributed system for analysis and monitoring (DSAM) of vibrations and acoustic noise, which consists of an array of intelligent modules, sensor modules, communication bus and a host PC acting as data center. The main advantages of the DSAM are its modularity, scalability, and flexibility for use of different type of sensors/transducers, with analog or digital outputs, and for signals of different nature. Its final cost is also significantly lower than other available commercial solutions. The system is reconfigurable, can operate either with synchronous or asynchronous modes, with programmable sampling frequencies, 8-bit or 12-bit resolution and a memory buffer of 15 kbyte. It allows real-time data-acquisition for signals of different nature, in applications that require a large number of sensors, thus it is suited for monitoring of vibrations in Linear Switched Reluctance Actuators (LSRAs). The acquired data allows the full characterization of the LSRA in terms of its response to vibrations of structural origins, and the vibrations and acoustic noise emitted under normal operation. The DSAM can also be used for electrical machine condition monitoring, machine fault diagnosis, structural characterization and monitoring, among other applications.

  1. Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite - CaBSiO4(OH)

    Science.gov (United States)

    Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Lima, Rosa Malena Fernandes; Horta, Laura Frota Campos; Lopez, Andres

    2013-11-01

    The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700-775 °C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077 cm-1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm-1 assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782 cm-1. The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms.

  2. An Intelligent Sensor Array Distributed System for Vibration Analysis and Acoustic Noise Characterization of a Linear Switched Reluctance Actuator

    Directory of Open Access Journals (Sweden)

    Maria Calado

    2012-06-01

    Full Text Available This paper proposes a distributed system for analysis and monitoring (DSAM of vibrations and acoustic noise, which consists of an array of intelligent modules, sensor modules, communication bus and a host PC acting as data center. The main advantages of the DSAM are its modularity, scalability, and flexibility for use of different type of sensors/transducers, with analog or digital outputs, and for signals of different nature. Its final cost is also significantly lower than other available commercial solutions. The system is reconfigurable, can operate either with synchronous or asynchronous modes, with programmable sampling frequencies, 8-bit or 12-bit resolution and a memory buffer of 15 kbyte. It allows real-time data-acquisition for signals of different nature, in applications that require a large number of sensors, thus it is suited for monitoring of vibrations in Linear Switched Reluctance Actuators (LSRAs. The acquired data allows the full characterization of the LSRA in terms of its response to vibrations of structural origins, and the vibrations and acoustic noise emitted under normal operation. The DSAM can also be used for electrical machine condition monitoring, machine fault diagnosis, structural characterization and monitoring, among other applications.

  3. Structural characterization of ammonium uranate by infrared spectroscopy

    International Nuclear Information System (INIS)

    Rodriguez S, A.

    1994-01-01

    Infrared spectroscopy have been used to investigate the chemical composition of some ammonium uranates. In this study, I have attempted to establish the interrelationship between the structure of the products, the character of their infrared spectra and x-ray diffraction data capable of consistent interpretation in terms of defining the compounds. (Author)

  4. Detailed characterization of anode-supported SOFCs by impedance spectroscopy

    DEFF Research Database (Denmark)

    Barfod, R.; Mogensen, Mogens Bjerg; Klemensø, Trine

    2007-01-01

    Anode-supported thin electrolyte cells are studied by electrochemical impedance spectroscopy (EIS). The aim is to describe how the losses of this type of cells are distributed at low current density (around open-circuit voltage) as a function of temperature. An equivalent circuit consisting...

  5. Characterization of Ge-nanocrystal films with photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Bostedt, C.; Buuren, T. van; Willey, T.M.; Nelson, A.J.; Franco, N.; Moeller, T.; Terminello, L.J.

    2003-01-01

    The Ge 3d core-levels of germanium nanocrystal films have been investigated by means of photoelectron spectroscopy. The experiments indicate bulk-like coordinated atoms in the nanocrystals and suggest structured disorder on the nanoparticle surface. The results underline the importance of the surface on the overall electronic structure of this class of nanostructured materials

  6. Characterization of a magnetic trap by polarization dependent Zeeman spectroscopy

    DEFF Research Database (Denmark)

    Nielsen, Carsten Vandel; Lyngsøe, Jens Kristian; Thorseth, Anders

    2008-01-01

    This paper demonstrates a detailed experimental study of our cloverleaf magnetic trap for sodium atoms. By using polarization dependent Zeeman spectroscopy of our atomic beam, passing the magnetic trap region, we have determined important trap parameters such as gradients, their curvatures...

  7. Analysis of structure and vibrational dynamics of the BeTe(001) surface using X-ray diffraction, Raman spectroscopy, and density functional theory

    DEFF Research Database (Denmark)

    Kumpf, C.; Müller, A.; Weigand, W.

    2003-01-01

    The atomic structure and lattice dynamics of epitaxial BeTe(001) thin films are derived from surface x-ray diffraction and Raman spectroscopy. On the Te-rich BeTe(001) surface [1 (1) over bar0]-oriented Te dimers are identified. They cause a (2 X 1) superstructure and induce a pronounced buckling...... in the underlying Te layer. The Be-rich surface exhibits a (4 X 1) periodicity with alternating Te dimers and Te-Be-Te trimers. A vibration eigenfrequency of 165 cm(-1) is observed for the Te-rich surface, while eigenmodes at 157 and 188 cm(-1) are found for the Be-rich surface. The experimentally derived atomic...... geometry and the vibration modes are in very good agreement with the results of density functional theory calculations....

  8. A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Nicholas H. C.; Dong, Hui; Oliver, Thomas A. A.; Fleming, Graham R., E-mail: grfleming@lbl.gov [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 (United States)

    2015-09-28

    Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

  9. Ultra violet resonance Raman spectroscopy in lignin analysis: determination of characteristic vibrations of p-hydroxyphenyl, guaiacyl, and syringyl lignin structures.

    Science.gov (United States)

    Saariaho, Anna-Maija; Jääskeläinen, Anna-Stiina; Nuopponen, Mari; Vuorinen, Tapani

    2003-01-01

    Raman spectroscopy of wood and lignin samples is preferably carried out in the near-infrared region because lignin produces an intense laser-induced fluorescence background at visible excitation wavelengths. However, excitation of aromatic and conjugated lignin structures with deep ultra violet (UV) light gives resonance-enhanced Raman signals while the overlapping fluorescence is eliminated. In this study, ultra violet resonance Raman (UVRR) spectroscopy was used to define characteristic vibration bands of model compounds of p-hydroxyphenyl, guaiacyl, and syringyl lignin structures at three excitation wavelengths (229, 244, and 257 nm). The intensities of each band, relative to the intensity of the aromatic vibration band at 1600 cm-1, were defined and the most suitable excitation wavelength was suggested for each structure. p-Hydroxyphenyl structures showed intensive characteristic bands at 1217-1214 and 1179-1167 cm-1 with excitation at 244 nm, whereas the bands of guaiacyl structures were more intensive with 257 nm excitation. Most intensive characteristic bands of guaiacyl structures were found at 1289-1279, 1187-1185, 1158-1155, and 791-704 cm-1. Syringyl structures had almost identical spectra with 244 and 257 nm excitations with characteristic bands at 1514-1506, 1333-1330, and 981-962 cm-1. The characteristic bands of the three structural units were also found from the compression wood, softwood, and hardwood samples, indicating that UVRR spectroscopy can be applied for the determination of chemical structures of lignin.

  10. Adsorption and Vibrational Study of Folic Acid on Gold Nanopillar Structures Using Surface-enhanced Raman Scattering Spectroscopy

    DEFF Research Database (Denmark)

    Castillo, John J.; Rindzevicius, Tomas; Rozo, Ciro E.

    2015-01-01

    on the nanopillars within the high electromagnetic field areas. The adsorption behaviour of folic acid and the band assignment of the main vibrations together with the optimized geometry of folic acid and folic acid in the presence of a cluster of 10 gold atoms were assessed using the density functional theory (B3......LYP(6-31G(d))) and the scalar relativistic effective core potential with a double-zeta basis set (LANL2DZ). The vibrations obtained from the solid-state folic acid and the folic acid on a gold cluster were in accordance with those observed experimentally. The analysis of the main vibrations indicated...

  11. Defect Characterization in Semiconductors with Positron Annihilation Spectroscopy

    Science.gov (United States)

    Tuomisto, Filip

    Positron annihilation spectroscopy is an experimental technique that allows the selective detection of vacancy defects in semiconductors, providing a means to both identify and quantify them. This chapter gives an introduction to the principles of the positron annihilation techniques and then discusses the physics of some interesting observations on vacancy defects related to growth and doping of semiconductors. Illustrative examples are selected from studies performed in silicon, III-nitrides, and ZnO.

  12. Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

  13. Structural determination of some uranyl compounds by vibrational spectroscopy; Determinacion estructural de algunos compuestos de uranilo por espectroscopia vibracional

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez S, A.; Martinez Q, E

    1990-07-15

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  14. In situ speciation of the functional groups at mineral/electrolyte interfaces by sum frequency vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Floersheimer, M.; Kruse, K.; Klenze, R.; Kim, J.I. [Institut fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, D-76021 Karlsruhe (Germany); Fanghaenel, Th. [Institut fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, D-76021 Karlsruhe (Germany); Physikalisch-Chemisches Institut, Ruprecht-Karls-Universitaet Heidelberg, Im Neuenheimer Feld 253, D-69120, Heidelberg (Germany)

    2005-07-01

    Full text of publication follows: In order to describe surface reactivity and adsorption/desorption processes on the molecular level, a large number of functional groups has been postulated. In most cases, however, a direct proof for the existence of these species in real aquatic environment is lacking because it is difficult to obtain chemical analytical information in situ under electrolyte with interface selectivity. Here we apply interface selective sum frequency (SF) vibrational spectroscopy to study the (001) and (110) surfaces of sapphire ({alpha}-Al{sub 2}O{sub 3}) under water between pH 4 and 12. This work is part of an ongoing fundamental study of the sorption mechanism of actinides on single crystals faces of sapphire by various experimental and theoretical techniques. Sapphire is used as a simple model for natural clay minerals and related iron phases. In the O-H stretch region of the infrared spectrum between 2800 and 4000 cm{sup -1}, we observe a surprisingly large number of 8 SF bands in total. Two of them are due to the polar ordered water film near the mineral surface which is well known from various aquatic interfaces. The other bands originate from up to 6 different aluminol species or from specifically [1] bound water molecules. The prominent peak of the (001) surface (SF intensity maximum at 3690 cm{sup -1}), we attribute to an OH species bridging two [1-4] aluminium atoms. At the (110) surface, the concentration of this species is considerably smaller. Another aluminol species that can be detected at the (001) and the (110) surface (signal maximum near 3450 cm{sup -1}) exhibits O-H bonds which are almost parallel to the interface plane. This species is probably the in-plane aluminol group predicted in recent molecular dynamics calculations [4]. SF spectroscopy allows us also to measure the absolute polar orientation of the water molecules adjacent to the mineral surface. The inversion of the molecules polar orientation upon alteration of the p

  15. Heterogeneous Dynamics of Coupled Vibrations

    NARCIS (Netherlands)

    Cringus, Dan; Jansen, Thomas I. C.; Pshenichnikov, Maxim S.; Schoenlein, RW; Corkum, P; DeSilvestri, S; Nelson, KA; Riedle, E

    2009-01-01

    Frequency-dependent dynamics of coupled stretch vibrations of a water molecule are revealed by 2D IR correlation spectroscopy. These are caused by non-Gaussian fluctuations of the environment around the individual OH stretch vibrations.

  16. Vibrational spectroscopy and electrophoresis as a "golden means" in monitoring of polysaccharides in medical plant and gels

    Science.gov (United States)

    Pielesz, A.

    In recent years, some bioactive polysaccharides isolated from natural sources have attracted much attention in the field of biochemistry and pharmacology. Of them, polysaccharides or their glycoconjugates were shown to exhibit multiple biological activities including anticarcinogenic, anticoagulant, immunostimulating, antioxidant, etc. Pharmacotherapy using plant-derived substances can be currently regarded as a very promising future alternative to conventional therapy. The advanced biotechnologies available today enable chemical investigation of well-defined bioactive plant components as sources of novel drugs. The need for safer drugs without side effects has led to the use of natural ingredients with proven safety. Special interest is focused on plant polysaccharides. This article attempts to review the current structural and conformational characterization of some importantly bioactive monosaccharides isolated from following plant cell-wall: Symphytum officinale (comfrey), Thymus pulegioides (thyme), Trigonella foenum-graecum L. (fenugreek), Tussilago farfara L. (coltsfoot), Hyssopus officinalis (hyssop), Althaea officinalis L. (marshmallow) and Equisetum arvense L. (horsetail). The chemical structures of monosaccharides were analysed using FTIR and Raman spectroscopies as well as cellulose acetate membrane electrophoresis (CAE). The dried plant samples were gently hydrolysed with sulphuric acid. The presence of glucuronic acid, galacturonic acid, alginic acid, glucose, mannose and xylose in the hydrolysates of reference substances and non-defatted plant films was proved. The possibility of a taxonomic classification of plant cell walls based on infrared and Raman spectroscopies and the use of spectral fingerprinting for authentication and detection of adulteration of products rich in cell-wall materials are discussed. Individual bands were selected to monitor the sugar content in medical plant cell walls and to confirm the identity of the analysed plants.

  17. Characterization of Friction Joints Subjected to High Levels of Random Vibration

    Science.gov (United States)

    deSantos, Omar; MacNeal, Paul

    2012-01-01

    This paper describes the test program in detail including test sample description, test procedures, and vibration test results of multiple test samples. The material pairs used in the experiment were Aluminum-Aluminum, Aluminum- Dicronite coated Aluminum, and Aluminum-Plasmadize coated Aluminum. Levels of vibration for each set of twelve samples of each material pairing were gradually increased until all samples experienced substantial displacement. Data was collected on 1) acceleration in all three axes, 2) relative static displacement between vibration runs utilizing photogrammetry techniques, and 3) surface galling and contaminant generation. This data was used to estimate the values of static friction during random vibratory motion when "stick-slip" occurs and compare these to static friction coefficients measured before and after vibration testing.

  18. Seat Vibration in Military Propeller Aircraft: Characterization, Exposure Assessment, and Mitigation

    National Research Council Canada - National Science Library

    Smith, Suzanne D

    2006-01-01

    There have been increasing reports of annoyance, fatigue, and even neck and back pain during prolonged operation of military propeller aircraft, where persistent multi-axis vibration occurs at higher...

  19. FFTF scale-model characterization of flow-induced vibrational response of reactor internals

    International Nuclear Information System (INIS)

    Ryan, J.A.; Julyk, L.J.

    1977-01-01

    As an integral part of the Fast Test Reactor Vibration Program for Reactor Internals, the flow-induced vibrational characteristics of scaled Fast Test Reactor core internal and peripheral components were assessed under scaled and simulated prototype flow conditions in the Hydraulic Core Mockup. The Hydraulic Core Mockup, a 0.285 geometric scale model, was designed to model the vibrational and hydraulic characteristics of the Fast Test Reactor. Model component vibrational characteristics were measured and determined over a range of 36 percent to 111 percent of the scaled prototype design flow. Selected model and prototype components were shaker tested to establish modal characteristics. The dynamic response of the Hydraulic Core Mockup components exhibited no anomalous flow-rate dependent or modal characteristics, and prototype response predictions were adjudged acceptable

  20. Blade Vibration Measurement System for Characterization of Closely Spaced Modes and Mistuning, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — There are several ongoing challenges in non-contacting blade vibration and stress measurement systems that can address closely spaced modes and blade-to-blade...

  1. Scale-model characterization of flow-induced vibrational response of FFTF reactor internals

    International Nuclear Information System (INIS)

    Ryan, J.A.; Mahoney, J.J.

    1980-10-01

    Fast Test Reactor core internal and peripheral components were assessed for flow-induced vibrational characteristics under scaled and simulated prototype flow conditions in the Hydraulic Core Mockup as an integral part of the Fast Test Reactor Vibration Program. The Hydraulic Core Mockup was an 0.285 geometric scale model of the Fast Test Reactor internals designed to simulate prototype vibrational and hydraulic characteristics. Using water to simulate sodium coolant, vibrational characteristics were measured and determined for selected model components over the scaled flow range of 36 to 110%. Additionally, in-situ shaker tests were conducted on selected Hydraulic Core Mockup outlet plenum components to establish modal characteristics. Most components exhibited resonant response at all test flow rates; however, the measured dynamic response was neither abnormal nor anomalously flow-rate dependent, and the predicted prototype components' response were deemed acceptable

  2. FFTF scale-model characterization of flow induced vibrational response of reactor internals

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, J A; Julyk, L J [Hanford Engineering Development Laboratory, Richland, WA (United States)

    1977-12-01

    As an integral part of the Fast Test Reactor Vibration Program for Reactor Internals, the flow-induced vibrational characteristics of scaled Fast Test Reactor core internal and peripheral components were assessed under scaled and simulated prototype flow conditions in the Hydraulic Core Mockup. The Hydraulic Core Mockup, a 0.285 geometric scale model, was designed to model the vibrational and hydraulic characteristics of the Fast Test Reactor. Model component vibrational characteristics were measured and determined over a range of 36% to 111% of the scaled prototype design flow. Selected model and prototype components were shaker tested to establish modal characteristics. The dynamic response of the Hydraulic Core Mockup components exhibited no anomalous flow-rate dependent or modal characteristics, and prototype response predictions were adjudged acceptable. (author)

  3. FFTF scale-model characterization of flow induced vibrational response of reactor internals

    International Nuclear Information System (INIS)

    Ryan, J.A.; Julyk, L.J.

    1977-01-01

    As an integral part of the Fast Test Reactor Vibration Program for Reactor Internals, the flow-induced vibrational characteristics of scaled Fast Test Reactor core internal and peripheral components were assessed under scaled and simulated prototype flow conditions in the Hydraulic Core Mockup. The Hydraulic Core Mockup, a 0.285 geometric scale model, was designed to model the vibrational and hydraulic characteristics of the Fast Test Reactor. Model component vibrational characteristics were measured and determined over a range of 36% to 111% of the scaled prototype design flow. Selected model and prototype components were shaker tested to establish modal characteristics. The dynamic response of the Hydraulic Core Mockup components exhibited no anomalous flow-rate dependent or modal characteristics, and prototype response predictions were adjudged acceptable. (author)

  4. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  5. Characterization of fossil remains using XRF, XPS and XAFS spectroscopies

    International Nuclear Information System (INIS)

    Zougrou, I M; Katsikini, M; Pinakidou, F; Paloura, E C; Brzhezinskaya, M; Papadopoulou, L; Vlachos, E; Tsoukala, E

    2016-01-01

    Synchrotron radiation micro-X-Ray Fluorescence (μ-XRF), X-ray photoelectron (XPS) and X-ray Absorption Fine Structure (XAFS) spectroscopies are applied for the study of paleontological findings. More specifically the costal plate of a gigantic terrestrial turtle Titanochelon bacharidisi and a fossilized coprolite of the cave spotted hyena Crocuta crocuta spelaea are studied. Ca L 2,3 -edge NEXAFS and Ca 2p XPS are applied for the identification and quantification of apatite and Ca containing minerals. XRF mapping and XAFS are employed for the study of the spatial distribution and speciation of the minerals related to the deposition environment. (paper)

  6. Electrochemical Characterization of a PEMEC Using Impedance Spectroscopy

    DEFF Research Database (Denmark)

    Elsøe, Katrine; Grahl-Madsen, L.; Hjelm, Johan

    2017-01-01

    In this study, electrochemical impedance spectroscopy (EIS) is applied in combination with cyclic voltammetry (CV) and current density – cell voltage curves (iV-curves) to investigate the processes contributing to the total impedance of a polymer electrolyte membrane electrolysis cell (PEMEC). i......V-curves were linear above 0.35 A cm−2 implying ohmic processes to be performance limiting, however the impedance spectra showed three arcs indicating three electrochemical reactions at these conditions not to be purely ohmic, but also to have capacitive properties. A hypothesis that the composite Ir...

  7. Characterization of oil-producing microalgae using Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Samek, Ota; Zemánek, Pavel; Jonáš, Alexandr; Telle, H.H.

    2011-01-01

    Roč. 8, č. 10 (2011), s. 701-709 ISSN 1612-2011 R&D Projects: GA MŠk OC08034; GA MŠk ED0017/01/01; GA ČR GAP205/11/1687 Grant - others:EC(XE) PERG 06-GA-2009-256526 Institutional research plan: CEZ:AV0Z20650511 Keywords : Raman spectroscopy * algae * lipids * biofuel * iodine value * microorganisms Subject RIV: BH - Optics, Masers, Lasers Impact factor: 9.970, year: 2011

  8. Optical characterization of semiconductors infrared, Raman, and photoluminescence spectroscopy

    CERN Document Server

    Perkowitz, Sidney

    1993-01-01

    This is the first book to explain, illustrate, and compare the most widely used methods in optics: photoluminescence, infrared spectroscopy, and Raman scattering. Written with non-experts in mind, the book develops the background needed to understand the why and how of each technique, but does not require special knowledge of semiconductors or optics. Each method is illustrated with numerous case studies. Practical information drawn from the authors experience is given to help establish optical facilities, including commercial sources for equipment, and experimental details. For industrial sci

  9. Breast phantom for mammary tissue characterization by near infrared spectroscopy

    International Nuclear Information System (INIS)

    Miranda, D A; Cristiano, K L; Gutiérrez, J C

    2013-01-01

    Breast cancer is a disease associated to a high morbidity and mortality in the entire world. In the study of early detection of breast cancer the development of phantom is so important. In this research we fabricate a breast phantom using a ballistic gel with special modifications to simulate a normal and abnormal human breast. Optical properties of woman breast in the near infrared region were modelled with the phantom we developed. The developed phantom was evaluated with near infrared spectroscopy in order to study its relation with breast tissue. A good optical behaviour was achieved with the model fabricated

  10. Characterization of Momordica charantia Ussing FT-IR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Attila Keseru

    2016-11-01

    In this paper, because earlier claim shows that the plant used as stomachic, carminative, tonic, antipyretic, antidiabetic, in rheumatoid arthritis and gout, the present investigation was carried to characterized a principal components of plant using FT-IR technique

  11. Catalyzed hydrogenation of nitrogen and ethylene on metal (Fe, Pt) single crystal surfaces and effects of coadsorption: A sum frequency generation vibrational spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Westerberg, Staffan Per Gustav [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    High-pressure catalytic reactions and associated processes, such as adsorption have been studied on a molecular level on single crystal surfaces. Sum Frequency Generation (SFG) vibrational spectroscopy together with Auger Electron Spectroscopy (AES), Temperature Programmed Desorption (TPD) and Gas Chromatography (GC) were used to investigate the nature of species on catalytic surfaces and to measure the catalytic reaction rates. Special attention has been directed at studying high-pressure reactions and in particular, ammonia synthesis in order to identify reaction intermediates and the influence of adsorbates on the surface during reaction conditions. The adsorption of gases N2, H2, O2 and NH3 that play a role in ammonia synthesis have been studied on the Fe(111) crystal surface by sum frequency generation vibrational spectroscopy using an integrated Ultra-High Vacuum (UHV)/high-pressure system. SFG spectra are presented for the dissociation intermediates, NH2 (~3325 cm-1) and NH (~3235 cm-1) under high pressure of ammonia (200 Torr) on the clean Fe(111) surface. Addition of 0.5 Torr of oxygen to 200 Torr of ammonia does not significantly change the bonding of dissociation intermediates to the surface. However, it leads to a phase change of nearly 180° between the resonant and non-resonant second order non-linear susceptibility of the surface, demonstrated by the reversal of the SFG spectral features. Heating the surface in the presence of 200 Torr ammonia and 0.5 Torr oxygen reduces the oxygen coverage, which can be seen from the SFG spectra as another relative phase change of 180°. The reduction of the oxide is also supported by Auger electron spectroscopy. The result suggests that the phase change of the spectral features could serve as a sensitive indicator of the chemical environment of the adsorbates.

  12. Characterization of alkali-metal and alkaline-earth nitrates by vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    Martínez, S.

    1992-09-01

    Full Text Available Infrared spectra of sodium and potassium alkaline-metal nitrates and magnesium and calcium alkali-earth nitrates in solid phase had been recorded in order to assign the fundamental bands. The influence of the dispersal médium (alkaline halide, employed in the solid sample preparation have been discussed. The quantitative measurements of the band in ten sities at 1387 cm-1 (present in the I.R. spectra of the four nitrates in KBr médium allowed us to determine the Lambert-Beer law slopes for each compound. These values are differents (bearing in mind experimental random errors, so we have could to affirm the nonexistence of solid solution between the nitrate and the alkaline halide médium. The L-B law obtained by us can be used for the Identification differentiation and quantitative analysis of these nitrates in solid phase, even if they are present in a very low concentration.

    Se ha realizado la asignación de los espectros infrarrojo (IR de los nitratos alcalinos, sódico y potásico, y de los alcalinotérreos, magnésico y cálcico, en estado sólido. Se ha visto la influencia del medio dispersante (haluro alcalino, utilizado en la preparación de la muestra sólida. El estudio cuantitativo de la absorbencia de la banda a 1.387 cm-1 (presente en los espectros IR de los cuatro nitratos en medio KBr permite determinar las pendientes de la Ley de Lambert-Beer Se comprueba que dichas pendientes son diferentes lo que conduce a poder afirmar que no se produce disolución sólida entre el KBr y el nitrato alcalino o alcalinotérreo. La determinación de la ley de Lambert-Beer permite la identificación y el análisis cualitativo y cuantitativo por espectroscopia IR de estos nitratos cuando están presentes en bajas concentraciones en muestras sólidas.

  13. Mid-infrared spectroscopy for characterization of Baltic amber (succinite)

    Science.gov (United States)

    Wagner-Wysiecka, Ewa

    2018-05-01

    Natural Baltic amber (succinite) is the most appreciated fossil resin of the rich cultural traditions dating back to prehistoric times. Its unequivocal identification is extremely important in many branches of science and trades including archeology, paleontology, chemistry and finally mineralogical and gemological societies. Current methods of modification of natural succinite are more and more sophisticated making the identification of natural Baltic amber often challenging. In article the systematic analytical approach for identification of natural and modified under different conditions succinite, using mid-infrared spectroscopy (transmission, Drifts and ATR techniques) is presented. The correlation between spectral characteristics and properties of succinite is discussed pointing that the understanding of the nature of changes is the key of identification of this precious material.

  14. The Moessbauer spectroscopy in the characterization of atmospheric corrosion products

    International Nuclear Information System (INIS)

    Hernandez Torres, D.; Leiva Ronda, P.; Gomez, J.; Ronda, M.

    1996-01-01

    A study of corrosion products on mild steel formed after 1 and 5 years exposure in two industrial coastal weathering stations in the Bay from Matanzas City, Cuba, has been carried out. Structural analysis was conducted using mainly transmission Moessbauer Spectroscopy and the X-ray diffraction as complementary technique. The main phases found in the specimen exposed to high chloride containing environment were: lepidocrocite (γ- FeOOH), goethite (α- FeOOH) and magnetite concentration was the lowest, the phases found were γ- FeOOH and α- FeOOH, and the phase transformation proposed was γ- FeOOh -> α- Fe-OOH. In this station were found also amorphous corrosion products. There amorphous phases could be responsible for the lowest levels of corrosion on steel in this station

  15. Highly vibrationally excited O2 molecules in low-pressure inductively-coupled plasmas detected by high sensitivity ultra-broad-band optical absorption spectroscopy

    Science.gov (United States)

    Foucher, Mickaël; Marinov, Daniil; Carbone, Emile; Chabert, Pascal; Booth, Jean-Paul

    2015-08-01

    Inductively-coupled plasmas in pure O2 (at pressures of 5-80 mTorr and radiofrequency power up to 500 W) were studied by optical absorption spectroscopy over the spectral range 200-450 nm, showing the presence of highly vibrationally excited O2 molecules (up to vʺ = 18) by Schumann-Runge band absorption. Analysis of the relative band intensities indicates a vibrational temperature up to 10,000 K, but these hot molecules only represent a fraction of the total O2 density. By analysing the (11-0) band at higher spectral resolution the O2 rotational temperature was also determined, and was found to increase with both pressure and power, reaching 900 K at 80 mTorr 500 W. These measurements were achieved using a new high-sensitivity ultra-broad-band absorption spectroscopy setup, based on a laser-plasma light source, achromatic optics and an aberration-corrected spectrograph. This setup allows the measurement of weak broadband absorbances due to a baseline variability lower than 2   ×   10-5 across a spectral range of 250 nm.

  16. Structural, vibrational and thermal characterization of phase transformation in L-histidinium bromide monohydrate single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Moura, G.M. [Universidade Federal do Maranhão, CCSST, Imperatriz, MA, 65900-410 (Brazil); Universidade Federal do Sul e Sudeste do Pará, ICEN, Marabá, PA 68505-080 (Brazil); Carvalho, J.O. [Universidade Federal do Maranhão, CCSST, Imperatriz, MA, 65900-410 (Brazil); Instituto Federal do Tocantins, Araguaína, TO, 77.826-170 (Brazil); Silva, M.C.D.; Façanha Filho, P.F. [Universidade Federal do Maranhão, CCSST, Imperatriz, MA, 65900-410 (Brazil); Santos, A.O. dos, E-mail: adenilson1@gmail.com [Universidade Federal do Maranhão, CCSST, Imperatriz, MA, 65900-410 (Brazil)

    2015-09-01

    L-Histidinium bromide monohydrate (LHBr) single crystal is a nonlinear optical material. In this work the high temperature phase transformation and the thermal stability of single crystals of LHBr was investigated by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, differential scanning calorimetry and Raman spectroscopy. The results showed the LHBr phase transformation of orthorhombic (P2{sub 1}2{sub 1}2{sub 1}) to monoclinic system (P 1 2 1) at 120 °C, with the lattice parameters a = 12.162(1) Å, b = 16.821(2) Å, c = 19.477(2) Å and β = 108.56(2)°. These techniques are complementary and confirm the structural phase transformation due to loss water of crystallization. - Highlights: • -histidinium bromide single crystal was grown by slow evaporation technique. • X-ray diffraction characterize the high-temperature phase transformation. • The structural phase transformation occur due to loss of water of crystallization. • The LHBr thermal expansion coefficients exhibit an anisotropic behavior.

  17. High-resolution sub-Doppler infrared spectroscopy of atmospherically relevant Criegee precursor CH2I radicals: CH2 stretch vibrations and "charge-sloshing" dynamics

    Science.gov (United States)

    Kortyna, A.; Lesko, D. M. B.; Nesbitt, D. J.

    2018-05-01

    The combination of a pulsed supersonic slit-discharge source and single-mode difference frequency direct absorption infrared spectroscopy permit first high resolution infrared study of the iodomethyl (CH2I) radical, with the CH2I radical species generated in a slit jet Ne/He discharge and cooled to 16 K in the supersonic expansion. Dual laser beam detection and collisional collimation in the slit expansion yield sub-Doppler linewidths (60 MHz), an absolute frequency calibration of 13 MHz, and absorbance sensitivities within a factor of two of the shot-noise limit. Fully rovibrationally resolved direct absorption spectra of the CH2 symmetric stretch mode (ν2) are obtained and fitted to a Watson asymmetric top Hamiltonian with electron spin-rotation coupling, providing precision rotational constants and spin-rotation tensor elements for the vibrationally excited state. Analysis of the asymmetric top rotational constants confirms a vibrationally averaged planar geometry in both the ground- and first-excited vibrational levels. Sub-Doppler resolution permits additional nuclear spin hyperfine structures to be observed, with splittings in excellent agreement with microwave measurements on the ground state. Spectroscopic data on CH2I facilitate systematic comparison with previous studies of halogen-substituted methyl radicals, with the periodic trends strongly correlated with the electronegativity of the halogen atom. Interestingly, we do not observe any asymmetric CH2 stretch transitions, despite S/N ≈ 25:1 on strongest lines in the corresponding symmetric CH2 stretch manifold. This dramatic reversal of the more typical 3:1 antisymmetric/symmetric CH2 stretch intensity ratio signals a vibrational transition moment poorly described by simple "bond-dipole" models. Instead, the data suggest that this anomalous intensity ratio arises from "charge sloshing" dynamics in the highly polar carbon-iodine bond, as supported by ab initio electron differential density plots and

  18. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.

    2013-01-31

    The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

  19. Enzyme Characterization in Microreactors by UV-Vis Spectroscopy

    DEFF Research Database (Denmark)

    Ringborg, Rolf Hoffmeyer; Krühne, Ulrich; Woodley, John

    for selection can at this point be improved by characterization of the enzyme performance where also inhibition and toxicity effects are taken into account. Enzyme characterization is here defined as the effect on initial rate of reaction with respect to pH, enzyme, substrate, co-substrate, product and co......-product concentration [2]. From this investigation, it will be possible to determine whether the enzyme meets the criteria for process requirements or not. The development of the process will determine the requirements and this can also reach a state of maturity that resolves obstacles, lowers criteria and paves......, as the enzyme resource is scarce at this point of development. In the case where the reaction operates with UV active components, UV can be used to detect compounds with high sensitivity supplemented by multivariate data analysis. The spectra are here decorrelated and regressed to yield concentrations...

  20. Precision atomic beam density characterization by diode laser absorption spectroscopy

    International Nuclear Information System (INIS)

    Oxley, Paul; Wihbey, Joseph

    2016-01-01

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10 −5 are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 10 4 atoms cm −3 . The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

  1. Characterization of Canadian coals by nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.; Ripmeester, J.

    1983-06-01

    Apparent aromaticities of a series of Canadian coals of different rank were estimated by solid state nuclear magnetic resonance spectroscopy. The aromaticities varied from 0.57 for a lignite up to 0.86 for a semi-anthracite coal. The aromaticities correlated well with fixed carbon and oxygen content of the coals as well as with the mean reflectance of the coals. Correlations were also established between aromaticities and the H/C and H/SUB/a/SUB/r/SUB/u/C/SUB/a/SUB/r ratios of the coals. Uncertainties in calculation of the hypothetical H/SUB/a/SUB/r/SUB/u/C/SUB/a/SUB/r ratios, from experimental data were pointed out. Structural parameters of the chars derived from the coals by pyrolysis at 535 C were, also, estimated. The H/C and H/SUB/a/SUB/r/SUB/u/C/SUB/a/SUB/r ratios of the chars were markedly lower than those of coals. This was complemented by higher apparent aromaticities of the chars compared with the coals. (21 refs.)

  2. Precision atomic beam density characterization by diode laser absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Oxley, Paul; Wihbey, Joseph [Physics Department, The College of the Holy Cross, Worcester, Massachusetts 01610 (United States)

    2016-09-15

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10{sup −5} are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 10{sup 4} atoms cm{sup −3}. The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

  3. Precision atomic beam density characterization by diode laser absorption spectroscopy.

    Science.gov (United States)

    Oxley, Paul; Wihbey, Joseph

    2016-09-01

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10 -5 are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 10 4 atoms cm -3 . The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

  4. Simulation of vibrational energy transfer in two-dimensional infrared spectroscopy of amide I and amide II modes in solution

    NARCIS (Netherlands)

    Bloem, Robbert; Dijkstra, Arend G.; Jansen, Thomas La Cour; Knoester, Jasper

    2008-01-01

    Population transfer between vibrational eigenstates is important for many phenomena in chemistry. In solution, this transfer is induced by fluctuations in molecular conformation as well as in the surrounding solvent. We develop a joint electrostatic density functional theory map that allows us to

  5. Computational molecular spectroscopy of X ˜ 2 Π NCS: Electronic properties and ro-vibrationally averaged structure

    Science.gov (United States)

    Hirano, Tsuneo; Nagashima, Umpei; Jensen, Per

    2018-04-01

    For NCS in the X ˜ 2 Π electronic ground state, three-dimensional potential energy surfaces (3D PESs) have been calculated ab initio at the core-valence, full-valence MR-SDCI+Q/[aug-cc-pCVQZ (N, C, S)] level of theory. The ab initio 3D PESs are employed in second-order-perturbation-theory and DVR3D calculations to obtain various molecular constants and ro-vibrationally averaged structures. The 3D PESs show that the X ˜ 2 Π NCS has its potential minimum at a linear configuration, and hence it is a "linear molecule." The equilibrium structure has re (N-C) = 1.1778 Å, re (C-S) = 1.6335 Å, and ∠e (N-C-S) = 180°. The ro-vibrationally averaged structure, determined as expectation values over DVR3D wavefunctions, has 〈 r (N-C)〉0 = 1.1836 Å, 〈 r (C-S)〉0 = 1.6356 Å, and 〈 ∠ (N-C-S)〉0 = 172.5°. Using these expectation values as the initial guess, a bent r0 structure having an 〈 ∠ (N-C-S)〉0 of 172.2° is deduced from the experimentally reported B0 values for NC32S and NC34S. Our previous prediction that a linear molecule, in any ro-vibrational state including the ro-vibrational ground state, is to be "observed" as being bent on ro-vibrational average, has been confirmed here theoretically through the expectation value for the bond-angle deviation from linearity, 〈 ρ bar 〉 , and experimentally through the interpretation of the experimentally derived rotational-constant values.

  6. Single-Crystalline cooperite (PtS): Crystal-Chemical characterization, ESR spectroscopy, and {sup 195}Pt NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rozhdestvina, V. I., E-mail: veronika@ascnet.ru; Ivanov, A. V.; Zaremba, M. A. [Far East Division, Russian Academy of Sciences, Institute of Geology and Nature Management (Russian Federation); Antsutkin, O. N.; Forsling, W. [Lulea University of Technology (Sweden)

    2008-05-15

    Single-crystalline cooperite (PtS) with a nearly stoichiometric composition was characterized in detail by X-ray diffraction, electron-probe X-ray microanalysis, and high-resolution scanning electron microscopy. For the first time it was demonstrated that {sup 195}Pt static and MAS NMR spectroscopy can be used for studying natural platinum minerals. The {sup 195}Pt chemical-shift tensor of cooperite was found to be consistent with the axial symmetry and is characterized by the following principal values: {delta}{sub xx} = -5920 ppm, {delta}{sub yy} = -3734 ppm, {delta}{sub zz} = +4023 ppm, and {delta}{sub iso} = -1850 ppm. According to the ESR data, the samples of cooperite contain copper(II), which is adsorbed on the surface during the layer-by-layer crystal growth and is not involved in the crystal lattice.

  7. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  8. Laminated helmet materials characterization by terahertz kinetics spectroscopy

    Science.gov (United States)

    Rahman, Anis; Rahman, Aunik K.

    2015-05-01

    High speed acquisition of reflected terahertz energy constitutes a kinetics spectrum that is an effective tool for layered materials' deformation characterization under ballistic impact. Here we describe utilizing the kinetics spectrum for quantifying a deformation event due to impact in material used for Soldier's helmet. The same technique may be utilized for real-time assessment of trauma by measuring the helmet wore by athletes. The deformation of a laminated material (e.g., a helmet) is dependent on the nature of impact and projectile; thus can uniquely characterize the impact condition leading to a diagnostic procedure based on the energy received by an athlete during an impact. We outline the calibration process for a given material under ballistic impact and then utilize the calibration for extracting physical parameters from the measured kinetics spectrum. Measured kinetics spectra are used to outline the method and rationale for extending the concept to a diagnosis tool. In particular, captured kinetics spectra from multilayered plates subjected to ballistic hit under experimental conditions by high speed digital acquisition system. An algorithm was devised to extract deformation and deformation velocity from which the energy received on the skull was estimated via laws of nonrelativistic motion. This energy is assumed to be related to actual injury conditions, thus forming a basis for determining whether the hit would cause concussion, trauma, or stigma. Such quantification may be used for diagnosing a Soldier's trauma condition in the field or that of an athlete's.

  9. PREFACE: Vibrations at surfaces Vibrations at surfaces

    Science.gov (United States)

    Rahman, Talat S.

    2011-12-01

    This special issue is dedicated to the phenomenon of vibrations at surfaces—a topic that was indispensible a couple of decades ago, since it was one of the few phenomena capable of revealing the nature of binding at solid surfaces. For clean surfaces, the frequencies of modes with characteristic displacement patterns revealed how surface geometry, as well as the nature of binding between atoms in the surface layers, could be different from that in the bulk solid. Dispersion of the surface phonons provided further measures of interatomic interactions. For chemisorbed molecules on surfaces, frequencies and dispersion of the vibrational modes were also critical for determining adsorption sites. In other words, vibrations at surfaces served as a reliable means of extracting information about surface structure, chemisorption and overlayer formation. Experimental techniques, such as electron energy loss spectroscopy and helium-atom-surface scattering, coupled with infra-red spectroscopy, were continually refined and their resolutions enhanced to capture subtleties in the dynamics of atoms and molecules at surfaces. Theoretical methods, whether based on empirical and semi-empirical interatomic potential or on ab initio electronic structure calculations, helped decipher experimental observations and provide deeper insights into the nature of the bond between atoms and molecules in regions of reduced symmetry, as encountered on solid surfaces. Vibrations at surfaces were thus an integral part of the set of phenomena that characterized surface science. Dedicated workshops and conferences were held to explore the variety of interesting and puzzling features revealed in experimental and theoretical investigations of surface vibrational modes and their dispersion. One such conference, Vibrations at Surfaces, first organized by Harald Ibach in Juelich in 1980, continues to this day. The 13th International Conference on Vibrations at Surfaces was held at the University of

  10. Characterizing Rosetta Stone Exoplanets with JWST Transit Spectroscopy

    Science.gov (United States)

    Lewis, Nikole K.; Clampin, Mark; Seager, Sara; Valenti, Jeff A.; Mountain, Matt; JWST Telescope Scientist GTO Team

    2017-06-01

    JWST will for the first time provide for spectroscopic (R > 100) observation of systems hosting transiting exoplanets over the critical wavelength range from 0.6 to 28.5 microns. Our team will take advantage of JWST's spectral coverage and resolution to characterize a small number of exoplanets in exquisite detail. We plan to focus our efforts on single representative members of the hot-Jupiter, warm-Neptune, and temperate-Earth populations in both transmission and emission over the full wavelength range of JWST. Our JWST observations will hopefully become 'Rosetta Stones' that will serve as benchmarks for further observations of planets within each representative population and a lasting legacy of the JWST mission. Here we will describe our observational plan and how we turned our science goals into an implemented Cycle 1 JWST program.

  11. Characterization of solar cell materials by Proton Back Scattering Spectroscopy

    International Nuclear Information System (INIS)

    Joynal Abedin, M.; Fazlul Hoque, A.K.M.; Firoz Hasan, S.M.

    2001-01-01

    The need for accurate chemical characterization of samples specially related to electronic and solar cell materials has assumed increasing importance in recent years. The importance of the study of the surfaces of materials of different origin also increased in recent years to a great extent. This need has created a worldwide spurt to develop rapid, accurate and sensitive tools for the characterization of materials. In recent years the proton backscattering spectrometry (PBS) method has been recognized as one of the useful analytical tool in several applications of material analysis and technology. The lack of information of the relevant scattering cross sections as a function of proton energy and the problems arising in conventional data analysis have so far rendered proton backscattering analysis of multielemental samples difficult at low energies. On the other hand advances in the computer evaluation of experimental data have, however, made it possible to utilize low-MeV protons as a sensitive probe for light elements in the μm range. The benefits of the method in comparison to alpha particle backscattering include the relatively higher non-Rutherford scattering cross sections of the light elements and to the lower proton stopping in the target material. These lead to higher sensitivity in detecting and profiling light elements in heavy targets and to significantly larger accessible depths and smaller straggling than with alpha particles. Research works on the development of methodologies of Proton Backscattering Spectrometry (PBS) for the analysis of thin films and surfaces has been in progress in the 3 MeV Van de Graaff Accelerator facilities of Atomic Energy Centre, Dhaka for some years. The PBS system comprises a target chamber with appropriate sample holders and a Surface Barrier Detector (SBD) with the associated electronics for data acquisition and reduction. For the evaluation of the PBS data RBS Universal Master Package, RUMP has been installed in the

  12. High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

    Science.gov (United States)

    Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

    2014-01-01

    High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

  13. Application of support vector regression for optimization of vibration flow field of high-density polyethylene melts characterized by small angle light scattering

    Science.gov (United States)

    Xian, Guangming

    2018-03-01

    In this paper, the vibration flow field parameters of polymer melts in a visual slit die are optimized by using intelligent algorithm. Experimental small angle light scattering (SALS) patterns are shown to characterize the processing process. In order to capture the scattered light, a polarizer and an analyzer are placed before and after the polymer melts. The results reported in this study are obtained using high-density polyethylene (HDPE) with rotation speed at 28 rpm. In addition, support vector regression (SVR) analytical method is introduced for optimization the parameters of vibration flow field. This work establishes the general applicability of SVR for predicting the optimal parameters of vibration flow field.

  14. Sum Frequency Generation Vibrational Spectroscopy Studies on ModelPeptide Adsorption at the Hydrophobic Solid-Water and HydrophilicSolid-Water Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    York, Roger L. [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilic peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a parameter that could change the peptide's secondary structure in solution. It was determined that on a hydrophobic surface, the peptide's interfacial structure was independent of its structure in solution. This was in contrast to the adsorbed structure on a hydrophilic surface, where the peptide's interfacial structure showed a strong dependence on its solution secondary structure. In a third experiment, the SFG spectra of lysine and proline amino acids on both hydrophobic and hydrophilic surfaces were obtained by using a different experimental geometry that increases the SFG signal

  15. Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere

    Science.gov (United States)

    Derro, Erika L.

    The hydrogen trioxy (HOOO) radical has been implicated as an important intermediate in key processes in the atmosphere. In the present studies, HOOO is produced by the combination of O2 and photolytically generated OH radicals in the collisional region of a pulsed supersonic expansion. Rotationally cooled HOOO is probed in the effectively collision-free region of the expansion using infrared action spectroscopy, an infrared-pump, ultraviolet-probe technique, in which HOOO is vibrationally excited and the nascent OH products of vibrational predissociation are probed via laser-induced fluorescence. High resolution infrared spectra of HOOO and DOOO were observed in the fundamental and overtone OH/D stretching regions (nui and 2nu 1), which comprise a rotationally structured band attributed to the trans conformer, and an unstructured component assigned to the cis conformer. Infrared spectra of HOOO and DOOO combination bands composed of the OH stretch and a low frequency mode (nu1 + nun) were also observed. This allowed identification of vibrational frequencies for five of the six modes for trans-H/DOOO and four of the six modes for cis-HOOO and DOOO. Identification of low frequency modes provides critical information on the vibrational dynamics and thermochemical properties of the HOOO radical, and furthermore, provides a potential means for detecting HOOO in situ in the atmosphere. In addition, the nascent OH X2pi products following vibrational predissociation of HOOO have been investigated. The product state distributions reveal a distinct preference for population of pi(A ') Λ-doublets in OH that is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained. The highest observed OH quantum state allows determination of the stability of HOOO relative to the OH + O 2 asymptote using a conservation of energy approach. In conjunction with a similar investigation of DOOO, the binding energy is determined to be ≤ 5

  16. Neutron resonance spectroscopy for the characterization of materials and objects

    International Nuclear Information System (INIS)

    Schillebeeckx, P; Borella, A; Emiliani, F; Kopecky, S; Lampoudis, C; Gorini, G; Cippo, E Perelli; Kockelmann, W; Rhodes, N J; Schooneveld, E M; Moxon, M; Postma, H; Van Beveren, C

    2012-01-01

    The resonance structure in neutron induced reaction cross sections can be used to determine the elemental compositions of materials or objects. The occurrence of resonances is the basis of neutron resonance capture analysis (NRCA) and neutron resonance transmission analysis (NRTA). NRCA and NRTA are fully non-destructive methods to determine the bulk elemental composition without the need of any sample preparation and resulting in a negligible residual activity. They have been applied to determine the elemental composition of archaeological objects and to characterize reference materials used for cross section measurements. For imaging applications a position sensitive neutron detector has been developed within the ANCIENT CHARM project. The detector is based on a 10 × 10 array of 6 Li-glass scintillators mounted on a pitch of 2.5 mm, resulting in a 25 × 25 mm 2 active area. The detector has been tested at the time-of-flight facility GELINA and used at the ISIS spallation source to study cultural heritage objects.

  17. Neutron resonance spectroscopy for the characterization of materials and objects

    Science.gov (United States)

    Schillebeeckx, P.; Borella, A.; Emiliani, F.; Gorini, G.; Kockelmann, W.; Kopecky, S.; Lampoudis, C.; Moxon, M.; Perelli Cippo, E.; Postma, H.; Rhodes, N. J.; Schooneveld, E. M.; Van Beveren, C.

    2012-03-01

    The resonance structure in neutron induced reaction cross sections can be used to determine the elemental compositions of materials or objects. The occurrence of resonances is the basis of neutron resonance capture analysis (NRCA) and neutron resonance transmission analysis (NRTA). NRCA and NRTA are fully non-destructive methods to determine the bulk elemental composition without the need of any sample preparation and resulting in a negligible residual activity. They have been applied to determine the elemental composition of archaeological objects and to characterize reference materials used for cross section measurements. For imaging applications a position sensitive neutron detector has been developed within the ANCIENT CHARM project. The detector is based on a 10 × 10 array of 6Li-glass scintillators mounted on a pitch of 2.5 mm, resulting in a 25 × 25 mm2 active area. The detector has been tested at the time-of-flight facility GELINA and used at the ISIS spallation source to study cultural heritage objects.

  18. Rotational and rovibrational spectroscopy of the v 8 = 1 and 2 vibrational states of CH3NC

    Czech Academy of Sciences Publication Activity Database

    Pracna, Petr; Urban, Jiří; Votava, Ondřej; Meltzerová, Z.; Urban, Š.; Horneman, V. M.

    2011-01-01

    Roč. 109, 17-18 (2011), s. 2237-2243 ISSN 0026-8976 R&D Projects: GA AV ČR IAA400400706; GA MŠk LC06071 Institutional research plan: CEZ:AV0Z40400503 Keywords : methyl isocyanide * high-resolution FTIR spectroscopy * submillimeter wave spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.819, year: 2011

  19. Experimental characterization of cantilever-type piezoelectric generator operating at resonance for vibration energy harvesting

    Energy Technology Data Exchange (ETDEWEB)

    Montanini, Roberto, E-mail: rmontanini@unime.it; Quattrocchi, Antonino, E-mail: aquattrocchi@unime.it [University of Messina, Dept. of Engineering, Contrada di Dio, Messina (Italy)

    2016-06-28

    A cantilever-type resonant piezoelectric generator (RPG) has been designed by gluing a PZT patch working in d{sub 31} mode onto a glass fibre reinforced composite cantilever beam with a discrete mass applied on its free end. The electrical and dynamic behaviour of the RPG prototype has been investigated by carrying out laboratory tests aimed to assess the effect of definite design parameters, specifically the electric resistance load and the excitation frequency. Results showed that an optimum resistance load exists, at which power generation is maximized. Moreover, it has been showed that power generation is strongly influenced by the vibration frequency highlighting that, at resonance, output power can be increased by more than one order of magnitude. Possible applications include inertial resonant harvester for energy recovery from vibrating machines, sea waves or wind flux and self-powering of wireless sensor nodes.

  20. Optical extinction spectroscopy used to characterize metallic nanowires

    International Nuclear Information System (INIS)

    Scaffardi, L B; Lester, M; Skigin, D; Tocho, J O

    2007-01-01

    We present a method for sizing metallic nanowires through the analysis of the extinction spectra of the scattered light when the wires are illuminated alternatively with p- and s-polarization waves. The method is applied to isolated silver nanowires in air or immersed in index matching oil. The dielectric function of silver is affected by the size of the cylinders, and its influence on the extinction spectra near the plasmon resonance or near the dip position is considered. Due to the size of the nanocylinders, it is necessary to include two different permittivities in the electromagnetic model to analyse the behaviour of the material under different polarization incidences. This introduces anisotropy in the system, which comprises isotropic cylinders. The behaviour of the extinction spectra for p-waves allows us to determine the wire radii, taking into account the plasmon peak position for radii larger than 7 nm, or alternatively, by using the contrast between maximum and minimum intensity near the plasmon frequency, for radii lower than 5 nm. For s-waves, although no plasmon peak appears, we can determine the radii by analysing the contrast between the ridge of the spectra near 260-275 nm and the minimum near 320-330 nm for radii larger than 10 nm, or analysing the slope in the spectra over 350 nm, for radii below 10 nm. The present study shows that spectral extinction is a very simple and inexpensive technique that can be useful for characterizing the radius of nanocylinders when electron microscopy (TEM or SEM) is not available

  1. Fabrication and vibration characterization of curcumin extracted from turmeric (Curcuma longa) rhizomes of the northern Vietnam

    OpenAIRE

    Van Nong, Hoang; Hung, Le Xuan; Thang, Pham Nam; Chinh, Vu Duc; Vu, Le Van; Dung, Phan Tien; Van Trung, Tran; Nga, Pham Thu

    2016-01-01

    In this report, we present the research results on using the conventional method and microwave technology to extract curcuminoid from turmeric roots originated in different regions of Northern Vietnam. This method is simple, yet economical, non-toxic and still able to achieve high extraction performance to get curcuminoid from turmeric roots. The detailed results on the Raman vibration spectra combined with X-ray powder diffraction and high-performance liquid chromatography/mass spectrometry ...

  2. Characterization and calibration of piezoelectric polymers: In situ measurements of body vibrations

    Science.gov (United States)

    Kappel, Marcel; Abel, Markus; Gerhard, Reimund

    2011-07-01

    Piezoelectric polymers are known for their flexibility in applications, mainly due to their bending ability, robustness, and variable sensor geometry. It is an optimal material for minimal-invasive investigations in vibrational systems, e.g., for wood, where acoustical impedance matches particularly well. Many applications may be imagined, e.g., monitoring of buildings, vehicles, machinery, alarm systems, such that our investigations may have a large impact on technology. Longitudinal piezoelectricity converts mechanical vibrations normal to the polymer-film plane into an electrical signal, and the respective piezoelectric coefficient needs to be carefully determined in dependence on the relevant material parameters. In order to evaluate efficiency and durability for piezopolymers, we use polyvinylidene fluoride and measure the piezoelectric coefficient with respect to static pressure, amplitude of the dynamically applied force, and long-term stability. A known problem is the slow relaxation of the material towards equilibrium, if the external pressure changes; here, we demonstrate how to counter this problem with careful calibration. Since our focus is on acoustical measurements, we determine accurately the frequency response curve - for acoustics probably the most important characteristic. Eventually, we show that our piezopolymer transducers can be used as a calibrated acoustical sensors for body vibration measurements on a wooden musical instrument, where it is important to perform minimal-invasive measurements. A comparison with the simultaneously recorded airborne sound yields important insight of the mechanism of sound radiation in comparison with the sound propagating in the material. This is especially important for transient signals, where not only the long-living eigenmodes contribute to the sound radiation. Our analyses support that piezopolymer sensors can be employed as a general tool for the determination of the internal dynamics of vibrating systems.

  3. Morphological, structural, thermal, compositional, vibrational, and pasting characterization of white, yellow, and purple Arracacha Lego-like starches and flours (Arracacia xanthorrhiza).

    Science.gov (United States)

    Londoño-Restrepo, Sandra M; Rincón-Londoño, Natalia; Contreras-Padilla, Margarita; Millan-Malo, Beatriz M; Rodriguez-Garcia, Mario E

    2018-07-01

    This work is focused on the chemical, structural, morphological, thermal, IR vibrational, and pasting characterization of isolated white, yellow, and purple Arracacha starches from Colombia. Inductive couple plasma showed that these starches are rich in potassium. Scanning Electron Microscopy (SEM) images show that the starch granules are formed by ovoid fully filled Lego-like starch microparticles, the circular cross-section has a diameter between 9 and 15μm and mayor axis between 20 and 30μm. Each one of these ovoids is formed by irregular wedge-shaped 6 to 10 isolated starch granules with an average size between 4 and 12μm. The amylose content ranged between 31 and 36%. Arracacha starches exhibited high viscosity values (between 20.000 and 28.000cP), which could be influenced by the high content of potassium ions, due to the C-H~K Van Der Waals interaction that was identified by using IR spectroscopy. According to the X-ray diffraction analysis, the starch patterns exhibited broad diffracted peaks which could be associated with the existence of nano-crystals and lamellae; the Differential Scanning calorimetry (DSC) result showed starches with a low gelatinization temperature of about 60°C. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Modeling and experimental characterization of a new piezoelectric sensor for low-amplitude vibration measurement

    International Nuclear Information System (INIS)

    Hou, X Y; Koh, C G; Kuang, K S C; Lee, W H

    2017-01-01

    This paper investigates the capability of a novel piezoelectric sensor for low-frequency and low-amplitude vibration measurement. The proposed design effectively amplifies the input acceleration via two amplifying mechanisms and thus eliminates the use of the external charge amplifier or conditioning amplifier typically employed for measurement system. The sensor is also self-powered, i.e. no external power unit is required. Consequently, wiring and electrical insulation for on-site measurement are considerably simpler. In addition, the design also greatly reduces the interference from rotational motion which often accompanies the translational acceleration to be measured. An analytical model is developed based on a set of piezoelectric constitutive equations and beam theory. Closed-form expression is derived to correlate sensor geometry and material properties with its dynamic performance. Experimental calibration is then carried out to validate the analytical model. After calibration, experiments are carried out to check the feasibility of the new sensor in structural vibration detection. From experimental results, it is concluded that the proposed sensor is suitable for measuring low-frequency and low-amplitude vibrations. (paper)

  5. Spectroscopy in catalysis : an introduction

    NARCIS (Netherlands)

    Niemantsverdriet, J.W.

    2000-01-01

    Spectroscopy in Catalysis describes the most important modern analytical techniques used to investigate catalytic surfaces. These include electron spectroscopy (XPS, UPS, AES, EELS), ion spectroscopy (SIMS, SNMS, RBS, LEIS), vibrational spectroscopy (infrared, Raman, EELS), temperature-programmed

  6. Overtone vibrational spectroscopy in H2-H2O complexes: a combined high level theoretical ab initio, dynamical and experimental study.

    Science.gov (United States)

    Ziemkiewicz, Michael P; Pluetzer, Christian; Nesbitt, David J; Scribano, Yohann; Faure, Alexandre; van der Avoird, Ad

    2012-08-28

    First results are reported on overtone (v(OH) = 2 ← 0) spectroscopy of weakly bound H(2)-H(2)O complexes in a slit supersonic jet, based on a novel combination of (i) vibrationally mediated predissociation of H(2)-H(2)O, followed by (ii) UV photodissociation of the resulting H(2)O, and (iii) UV laser induced fluorescence on the nascent OH radical. In addition, intermolecular dynamical calculations are performed in full 5D on the recent ab initio intermolecular potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008)] in order to further elucidate the identity of the infrared transitions detected. Excellent agreement is achieved between experimental and theoretical spectral predictions for the most strongly bound van der Waals complex consisting of ortho (I = 1) H(2) and ortho (I = 1) H(2)O (oH(2)-oH(2)O). Specifically, two distinct bands are seen in the oH(2)-oH(2)O spectrum, corresponding to internal rotor states in the upper vibrational manifold of Σ and Π rotational character. However, none of the three other possible nuclear spin modifications (pH(2)-oH(2)O, pH(2)-pH(2)O, or oH(2)-pH(2)O) are observed above current signal to noise level, which for the pH(2) complexes is argued to arise from displacement by oH(2) in the expansion mixture to preferentially form the more strongly bound species. Direct measurement of oH(2)-oH(2)O vibrational predissociation in the time domain reveals lifetimes of 15(2) ns and <5(2) ns for the Σ and Π states, respectively. Theoretical calculations permit the results to be interpreted in terms of near resonant energy levels and intermolecular alignment of the H(2) and H(2)O wavefunctions, providing insight into predissociation dynamical pathways from these metastable levels.

  7. FT-IR, FT-Raman, UV-visible, and NMR spectroscopy and vibrational properties of the labdane-type diterpene 13-epi-sclareol.

    Science.gov (United States)

    Chain, Fernando E; Leyton, Patricio; Paipa, Carolina; Fortuna, Mario; Brandán, Silvia A

    2015-03-05

    In this work, FT-IR, FT-Raman, UV-Visible and NMR spectroscopies and density functional theory (DFT) calculations were employed to study the structural and vibrational properties of the labdane-type diterpene 13-epi-sclareol using the hybrid B3LYP method together with the 6-31G(∗) basis set. Three stable structures with minimum energy found on the potential energy curves (PES) were optimized, and the corresponding molecular electrostatic potentials, atomic charges, bond orders, stabilization energies and topological properties were computed at the same approximation level. The complete assignment of the bands observed in the vibrational spectrum of 13-epi-sclareol was performed taking into account the internal symmetry coordinates for the three structures using the scaled quantum mechanical force field (SQMFF) methodology at the same level of theory. In addition, the force constants were calculated and compared with those reported in the literature for similar compounds. The predicted vibrational spectrum and the calculated (1)H NMR and (13)C NMR chemical shifts are in good agreement with the corresponding experimental results. The theoretical UV-Vis spectra for the most stable structure of 13-epi-sclareol demonstrate a better correlation with the corresponding experimental spectrum. The study of the three conformers by means of the theory of atoms in molecules (AIM) revealed different H bond interactions and a strong dependence of the interactions on the distance between the involved atoms. Furthermore, the natural bond orbital (NBO) calculations showed the characteristics of the electronic delocalization for the two six-membered rings with chair conformations. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Vibrational spectroscopy of the phosphate mineral lazulite--(Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil.

    Science.gov (United States)

    Frost, Ray L; Xi, Yunfei; Beganovic, Martina; Belotti, Fernanda Maria; Scholz, Ricardo

    2013-04-15

    This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm(-1) assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO4(2-) units. Two Raman bands at 1102 and 1137 cm(-1) are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm(-1) are attributed to the ν1PO4(3-) symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm(-1) are assigned to the ν3PO4(3-) antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm(-1) are assigned to the ν4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm(-1) are attributed to the ν2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm(-1) are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Proton conducting system (ImH2)2SeO4·2H2O investigated with vibrational spectroscopy

    Science.gov (United States)

    Zięba, Sylwia; Mizera, Adam; Pogorzelec-Glaser, Katarzyna; Łapiński, Andrzej

    2017-06-01

    Imidazolium selenate dihydrate (ImH2)2SeO4·2H2O crystals have been investigated using Raman and IR spectroscopy. Experimental data were supported by the quantum-chemical calculations (DFT), Hirshfield surfaces and fingerprint plots analysis, and Bader theory calculations. The imidazolium selenate dihydrate crystal exhibits high proton conductivity of the order of 10- 1 S/m at T = 333 K. The spectra of this compound are dominated by bands related to the lattice modes, the internal vibrations of the protonated imidazole cation, selenate anion, water molecules, and hydrogen bonds network. For the imidazolium selenate dihydrate crystal, the formal classification of the fundamental modes has been carried out.

  10. Amine Chemistry at Aqueous Interfaces: The Study of Organic Amines in Neutralizing Acidic Gases at an Air/Water Surface Using Vibrational Sum Frequency Spectroscopy

    Science.gov (United States)

    McWilliams, L.; Wren, S. N.; Valley, N. A.; Richmond, G.

    2014-12-01

    Small organic bases have been measured in atmospheric samples, with their sources ranging from industrial processing to animal husbandry. These small organic amines are often highly soluble, being found in atmospheric condensed phases such as fogwater and rainwater. Additionally, they display acid-neutralization ability often greater than ammonia, yet little is known regarding their kinetic and thermodynamic properties. This presentation will describe the molecular level details of a model amine system at the vapor/liquid interface in the presence of acidic gas. We find that this amine system shows very unique properties in terms of its bonding, structure, and orientation at aqueous surfaces. The results of our studies using a combination of computation, vibrational sum frequency spectroscopy, and surface tension will report the properties inherent to these atmospherically relevant species at aqueous surfaces.

  11. Sum Frequency Generation Vibrational Spectroscopy and Kinetic Study of 2-Methylfuran and 2,5-Dimethylfuran Hydrogenation over 7 nm Platinum Cubic Nanoparticles

    KAUST Repository

    Aliaga, Cesar

    2011-04-28

    Sum frequency generation vibrational spectroscopy and kinetic measurements obtained from gas chromatography were used to study the adsorption and hydrogenation of 2-methylfuran (MF) and 2,5-dimethylfuran (DMF) over cubic Pt nanoparticles of 7 nm average size, synthesized by colloidal methods and cleaned by ultraviolet light and ozone treatment. Reactions carried out at atmospheric pressure in the temperature range of 20-120 °C produced dihydro and tetrahydro species, as well as ring-opening products (alcohols) and ring-cracking products, showing high selectivity toward ring opening throughout the entire temperature range. The aromatic rings (MF and DMF) adsorbed parallel to the nanoparticle surface. Results yield insight into various surface reaction intermediates and the reason for the significantly lower selectivity for ring cracking in DMF hydrogenation compared to MF hydrogenation. © 2011 American Chemical Society.

  12. Bio-functions and molecular carbohydrate structure association study in forage with different source origins revealed using non-destructive vibrational molecular spectroscopy techniques.

    Science.gov (United States)

    Ji, Cuiying; Zhang, Xuewei; Yan, Xiaogang; Mostafizar Rahman, M; Prates, Luciana L; Yu, Peiqiang

    2017-08-05

    The objectives of this study were to: 1) investigate forage carbohydrate molecular structure profiles; 2) bio-functions in terms of CHO rumen degradation characteristics and hourly effective degradation ratio of N to OM (HED N/OM ), and 3) quantify interactive association between molecular structures, bio-functions and nutrient availability. The vibrational molecular spectroscopy was applied to investigate the structure feature on a molecular basis. Two sourced-origin alfalfa forages were used as modeled forages. The results showed that the carbohydrate molecular structure profiles were highly linked to the bio-functions in terms of rumen degradation characteristics and hourly effective degradation ratio. The molecular spectroscopic technique can be used to detect forage carbohydrate structure features on a molecular basis and can be used to study interactive association between forage molecular structure and bio-functions. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Vibrational spectroscopic characterisation of salmeterol xinafoate polymorphs and a preliminary investigation of their transformation using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Ali, Hassan Refat H. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom); Edwards, Howell G.M. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom)], E-mail: H.G.M.Edwards@bradford.ac.uk; Hargreaves, Michael D.; Munshi, Tasnim; Scowen, Ian J.; Telford, Richard J. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom)

    2008-07-14

    Knowledge and control of the polymorphic phases of chemical compounds are important aspects of drug development in the pharmaceutical industry. Salmeterol xinafoate, a long acting {beta}-adrenergic receptor agonist, exists in two polymorphic Forms, I and II. Raman and near infrared spectra were obtained of these polymorphs at selected wavelengths in the range of 488-1064 nm; significant differences in the Raman and near-infrared spectra were apparent and key spectral marker bands have been identified for the vibrational spectroscopic characterisation of the individual polymorphs which were also characterised with X ray diffractometry. The solid-state transition of salmeterol xinafoate polymorphs was studied using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry isothermally between transitions. This method assisted in the unambiguous characterisation of the two polymorphic forms by providing a simultaneous probe of both the thermal and vibrational data. The study demonstrates the value of a rapid in situ analysis of a drug polymorph which can be of potential value for at-line in-process control.

  14. Probing electron density of H-bonding between cation-anion of imidazolium-based ionic liquids with different anions by vibrational spectroscopy.

    Science.gov (United States)

    Gao, Yan; Zhang, Liqun; Wang, Yong; Li, Haoran

    2010-03-04

    Attenuated total reflection infrared spectroscopy and density functional theory calculation have been employed to study the spectral properties of imidazolium-based ionic liquids (ILs) with different anions. ILs based on 1-butyl-3-methylimidazolium cation with different anions, OH(-), CF(3)CO(2)(-), HSO(4)(-), H(2)PO(4)(-), Cl(-), PF(6)(-), and BF(4)(-), are investigated in the present work. It has been shown that the C(2)-H stretching vibration of the imidazolium ring is closely related to the electron density of H-bonding between the two closest cations and anions for pure ILs. The electron density of H-bonding between cation and anion with different anions decreases in the order [OH](-) > [H(2)PO(4)](-) > [HSO(4)](-) > [CF(3)CO(2)](-) > [Cl](-) > [BF(4)](-) > [PF(6)](-). For aqueous ILs, with increasing water content, the aromatic C-H stretching vibration of the imidazolium cation showed systematic blue-shifts. Especially for BmimOH, the nu(C(2))(-H) undergoes a drastic blue-shift by 58 cm(-1), suggesting that the formation of the strong hydrogen bonds O-H...O may greatly weaken the electron density of H-bonding between the cation and anion of ILs.

  15. Vibrational spectroscopic characterisation of salmeterol xinafoate polymorphs and a preliminary investigation of their transformation using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry

    International Nuclear Information System (INIS)

    Ali, Hassan Refat H.; Edwards, Howell G.M.; Hargreaves, Michael D.; Munshi, Tasnim; Scowen, Ian J.; Telford, Richard J.

    2008-01-01

    Knowledge and control of the polymorphic phases of chemical compounds are important aspects of drug development in the pharmaceutical industry. Salmeterol xinafoate, a long acting β-adrenergic receptor agonist, exists in two polymorphic Forms, I and II. Raman and near infrared spectra were obtained of these polymorphs at selected wavelengths in the range of 488-1064 nm; significant differences in the Raman and near-infrared spectra were apparent and key spectral marker bands have been identified for the vibrational spectroscopic characterisation of the individual polymorphs which were also characterised with X ray diffractometry. The solid-state transition of salmeterol xinafoate polymorphs was studied using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry isothermally between transitions. This method assisted in the unambiguous characterisation of the two polymorphic forms by providing a simultaneous probe of both the thermal and vibrational data. The study demonstrates the value of a rapid in situ analysis of a drug polymorph which can be of potential value for at-line in-process control

  16. Sub-Doppler spectroscopy of thioformaldehyde: Excited state perturbations and evidence for rotation-induced vibrational mixing in the ground state

    International Nuclear Information System (INIS)

    Clouthier, D.J.; Huang, G.; Adam, A.G.; Merer, A.J.

    1994-01-01

    High-resolution intracavity dye laser spectroscopy has been used to obtain sub-Doppler spectra of transitions to 350 rotational levels in the 4 1 0 band of the A 1 A 2 --X 1 A 1 electronic transition of thioformaldehyde. Ground state combination differences from the sub-Doppler spectra, combined with microwave and infrared data, have been used to improve the ground state rotational and centrifugal distortion constants of H 2 CS. The upper state shows a remarkable number of perturbations. The largest of these are caused by nearby triplet levels, with matrix elements of 0.05--0.15 cm -1 . A particularly clear singlet--triplet avoided crossing in K a ' = 7 has been shown to be caused by interaction with the F 1 component of the 3 1 6 2 vibrational level of the a 3 A 2 state. At least 53% of the S 1 levels show evidence of very small perturbations by high rovibronic levels of the ground state. The number of such perturbations is small at low J, but increases rapidly beyond J=5 such that 40%--80% of the observed S 1 levels of any given J are perturbed by ground state levels. Model calculations show that the density and J dependence of the number of perturbed levels can be explained if there is extensive rotation-induced mixing of the vibrational levels in the ground state

  17. New Insight into the Local Structure of Hydrous Ferric Arsenate Using Full-Potential Multiple Scattering Analysis, Density Functional Theory Calculations, and Vibrational Spectroscopy.

    Science.gov (United States)

    Wang, Shaofeng; Ma, Xu; Zhang, Guoqing; Jia, Yongfeng; Hatada, Keisuke

    2016-11-15

    Hydrous ferric arsenate (HFA) is an important arsenic-bearing precipitate in the mining-impacted environment and hydrometallurgical tailings. However, there is no agreement on its local atomic structure. The local structure of HFA was reprobed by employing a full-potential multiple scattering (FPMS) analysis, density functional theory (DFT) calculations, and vibrational spectroscopy. The FPMS simulations indicated that the coordination number of the As-Fe, Fe-As, or both in HFA was approximately two. The DFT calculations constructed a structure of HFA with the formula of Fe(HAsO 4 ) x (H 2 AsO 4 ) 1-x (OH) y ·zH 2 O. The presence of protonated arsenate in HFA was also evidenced by vibrational spectroscopy. The As and Fe K-edge X-ray absorption near-edge structure spectra of HFA were accurately reproduced by FPMS simulations using the chain structure, which was also a reasonable model for extended X-Ray absorption fine structure fitting. The FPMS refinements indicated that the interatomic Fe-Fe distance was approximately 5.2 Å, consistent with that obtained by Mikutta et al. (Environ. Sci. Technol. 2013, 47 (7), 3122-3131) using wavelet analysis. All of the results suggested that HFA was more likely to occur as a chain with AsO 4 tetrahedra and FeO 6 octahedra connecting alternately in an isolated bidentate-type fashion. This finding is of significance for understanding the fate of arsenic and the formation of ferric arsenate minerals in an acidic environment.

  18. Characterization of Modified and Polymer Coated Alumina Surfaces by Infrared Spectroscopy

    Directory of Open Access Journals (Sweden)

    Ashraf Yehia El-Naggar

    2013-01-01

    Full Text Available The prepared, modified, and coated alumina surfaces were characterized by infrared spectroscopy (FTIR to investigate the surface properties of the individual and double modified samples. FTIR helps in reporting the changes occurred in hydroxyl groups as well as the structure changes as a result of thermal treating, hydrothermal treating, silylation treating, alkali metal treating, coating, and bonding with polymer. FTIR spectroscopy represents the strength and abundance of surface acidic OH which determine the adsorption properties of polar and nonpolar sorbents. Generally, all treated samples exhibit decrease of OH groups compared with those of parent ones producing alumina surfaces of different adsorptive powers.

  19. Mössbauer and infrared spectroscopy as a diagnostic tool for the characterization of ferric tannates

    Science.gov (United States)

    Jaén, Juan A.; Navarro, César

    2009-07-01

    Fourier transform infrared spectroscopy and Mössbauer spectroscopy are use for the characterization and qualitative analysis of hydrolysable and condensed tannates. The two classes of tannates may be differentiated from the characteristic IR pattern. Mössbauer proof that a mixture of mono- and bis-type ferric tannate complexes, and an iron(II)-tannin complex are obtained from the interaction of hydrolysable tannins (tannic acid and chestnut tannin) and condensed tannins (mimosa and quebracho) with a ferric nitrate solution. At pH 7, a partially hydrolyzed ferric tannate complex was also obtained.

  20. Moessbauer and infrared spectroscopy as a diagnostic tool for the characterization of ferric tannates

    International Nuclear Information System (INIS)

    Jaen, Juan A.; Navarro, Cesar

    2009-01-01

    Fourier transform infrared spectroscopy and Moessbauer spectroscopy are use for the characterization and qualitative analysis of hydrolysable and condensed tannates. The two classes of tannates may be differentiated from the characteristic IR pattern. Moessbauer proof that a mixture of mono- and bis-type ferric tannate complexes, and an iron(II)-tannin complex are obtained from the interaction of hydrolysable tannins (tannic acid and chestnut tannin) and condensed tannins (mimosa and quebracho) with a ferric nitrate solution. At pH 7, a partially hydrolyzed ferric tannate complex was also obtained.

  1. Moessbauer and infrared spectroscopy as a diagnostic tool for the characterization of ferric tannates

    Energy Technology Data Exchange (ETDEWEB)

    Jaen, Juan A., E-mail: jjaen@ancon.up.ac.p [Universidad de Panama, Depto. de Quimica Fisica, CITEN, Lab. No. 105, Edificio de Laboratorios Cientificos-VIP (Panama); Navarro, Cesar [Universidad de Panama, Escuela de Quimica, Facultad de Ciencias Naturales, Exactas y Tecnologia (Panama)

    2009-07-15

    Fourier transform infrared spectroscopy and Moessbauer spectroscopy are use for the characterization and qualitative analysis of hydrolysable and condensed tannates. The two classes of tannates may be differentiated from the characteristic IR pattern. Moessbauer proof that a mixture of mono- and bis-type ferric tannate complexes, and an iron(II)-tannin complex are obtained from the interaction of hydrolysable tannins (tannic acid and chestnut tannin) and condensed tannins (mimosa and quebracho) with a ferric nitrate solution. At pH 7, a partially hydrolyzed ferric tannate complex was also obtained.

  2. Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Beni, A [Dipartimento di Chimica, Universita di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence (Italy); Bogani, L [Dipartimento di Chimica, Universita di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence (Italy); Bussotti, L [LENS, Universita di Firenze, Via Nello Carrara 1, 50019 Sesto Fiorentino, Florence (Italy); Dei, A [Dipartimento di Chimica, Universita di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence (Italy); Gentili, P L [LENS, Universita di Firenze, Via Nello Carrara 1, 50019 Sesto Fiorentino, Florence (Italy); Righini, R [Dipartimento di Chimica, Universita di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence (Italy)

    2005-01-01

    The valence tautomerism of low-spin Co{sup III}(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin Co{sup II}(Cat-N-BQ){sub 2} that, secondly, reaches the chemical equilibrium with the reactant species.

  3. Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

    International Nuclear Information System (INIS)

    Beni, A; Bogani, L; Bussotti, L; Dei, A; Gentili, P L; Righini, R

    2005-01-01

    The valence tautomerism of low-spin Co III (Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin Co II (Cat-N-BQ) 2 that, secondly, reaches the chemical equilibrium with the reactant species

  4. Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

    Science.gov (United States)

    Beni, A.; Bogani, L.; Bussotti, L.; Dei, A.; Gentili, P. L.; Righini, R.

    2005-01-01

    The valence tautomerism of low-spin CoIII(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin CoII(Cat-N-BQ)2 that, secondly, reaches the chemical equilibrium with the reactant species.

  5. Coherent vibrational dynamics

    CERN Document Server

    Lanzani, Guglielmo; De Silvestri, Sandro

    2007-01-01

    Vibrational spectroscopy is a powerful investigation tool for a wide class of materials covering diverse areas in physics, chemistry and biology. The continuous development in the laser field regarding ultrashort pulse generation has led to the possibility of producing light pulses that can follow vibrational motion coupled to the electronic transitions in molecules and solids in real time. Aimed at researchers and graduate students using vibrational spectroscopy, this book provides both introductory chapters as well as more advanced contents reporting on recent progress. It also provides a good starting point for scientists seeking a sound introduction to ultrafast optics and spectroscopic techniques.

  6. Far-infrared high resolution synchrotron FTIR spectroscopy of the ν11 bending vibrational fundamental transition of dimethylsulfoxyde

    Science.gov (United States)

    Cuisset, Arnaud; Nanobashvili, Lia; Smirnova, Irina; Bocquet, Robin; Hindle, Francis; Mouret, Gaël; Pirali, Olivier; Roy, Pascale; Sadovskií, Dmitrií A.

    2010-05-01

    We report the first successful high resolution gas phase study of the 'parallel' band of DMSO at 380 cm -1 associated with the ν11 bending vibrational mode. The spectrum was recorded with a resolution of 0.0015 cm -1 using the AILES beamline of the SOLEIL synchrotron source, the IFS 125 FTIR spectrometer and a multipass cell providing an optical path of 150 m. The rotational constants and centrifugal corrections obtained from the analysis of the resolved rotational transitions reproduce the spectrum to the experimental accuracy.

  7. An effective parameter optimization technique for vibration flow field characterization of PP melts via LS-SVM combined with SALS in an electromagnetism dynamic extruder

    Science.gov (United States)

    Xian, Guangming

    2018-03-01

    A method for predicting the optimal vibration field parameters by least square support vector machine (LS-SVM) is presented in this paper. One convenient and commonly used technique for characterizing the the vibration flow field of polymer melts films is small angle light scattering (SALS) in a visualized slit die of the electromagnetism dynamic extruder. The optimal value of vibration vibration frequency, vibration amplitude, and the maximum light intensity projection area can be obtained by using LS-SVM for prediction. For illustrating this method and show its validity, the flowing material is used with polypropylene (PP) and fifteen samples are tested at the rotation speed of screw at 36rpm. This paper first describes the apparatus of SALS to perform the experiments, then gives the theoretical basis of this new method, and detail the experimental results for parameter prediction of vibration flow field. It is demonstrated that it is possible to use the method of SALS and obtain detailed information on optimal parameter of vibration flow field of PP melts by LS-SVM.

  8. Molecular couplings and energy exchange between DNA and water mapped by femtosecond infrared spectroscopy of backbone vibrations

    Directory of Open Access Journals (Sweden)

    Yingliang Liu

    2017-07-01

    Full Text Available Molecular couplings between DNA and water together with the accompanying processes of energy exchange are mapped via the ultrafast response of DNA backbone vibrations after OH stretch excitation of the water shell. Native salmon testes DNA is studied in femtosecond pump-probe experiments under conditions of full hydration and at a reduced hydration level with two water layers around the double helix. Independent of their local hydration patterns, all backbone vibrations in the frequency range from 940 to 1120 cm–1 display a quasi-instantaneous reshaping of the spectral envelopes of their fundamental absorption bands upon excitation of the water shell. The subsequent reshaping kinetics encompass a one-picosecond component, reflecting the formation of a hot ground state of the water shell, and a slower contribution on a time scale of tens of picoseconds. Such results are benchmarked by measurements with resonant excitation of the backbone modes, resulting in distinctly different absorption changes. We assign the fast changes of DNA absorption after OH stretch excitation to structural changes in the water shell which couple to DNA through the local electric fields. The second slower process is attributed to a flow of excess energy from the water shell into DNA, establishing a common heated ground state in the molecular ensemble. This interpretation is supported by theoretical calculations of the electric fields exerted by the water shell at different temperatures.

  9. High resolution spectroscopy of 1,2-difluoroethane in a molecular beam: A case study of vibrational mode-coupling

    Science.gov (United States)

    Mork, Steven W.; Miller, C. Cameron; Philips, Laura A.

    1992-09-01

    The high resolution infrared spectrum of 1,2-difluoroethane (DFE) in a molecular beam has been obtained over the 2978-2996 cm-1 spectral region. This region corresponds to the symmetric combination of asymmetric C-H stretches in DFE. Observed rotational fine structure indicates that this C-H stretch is undergoing vibrational mode coupling to a single dark mode. The dark mode is split by approximately 19 cm-1 due to tunneling between the two identical gauche conformers. The mechanism of the coupling is largely anharmonic with a minor component of B/C plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. Analysis of the fine structure identifies the dark state as being composed of C-C torsion, CCF bend, and CH2 rock. Coupling between the C-H stretches and the C-C torsion is of particular interest because DFE has been observed to undergo vibrationally induced isomerization from the gauche to trans conformer upon excitation of the C-H stretch.

  10. Characterization of ZnO nanostructures: A challenge to positron annihilation spectroscopy and other methods

    Energy Technology Data Exchange (ETDEWEB)

    Brauer, Gerhard; Anwand, Wolfgang; Grambole, Dieter; Skorupa, Wolfgang [Institut fuer Ionenstrahlphysik und Materialforschung, Forschungszentrum Dresden-Rossendorf, Dresden (Germany); Egger, Werner; Sperr, Peter [Institut fuer Angewandte Physik und Messtechnik LRT2, Fakultaet fuer Luft- und Raumfahrttechnik, Werner-Heisenberg-Weg 39, Universitaet der Bundeswehr, Neubiberg (Germany); Beinik, Igor; Wang, Lin; Teichert, Christian [Institut fuer Physik, Montanuniversitaet Leoben (Austria); Kuriplach, Jan; Lang, Jan [Department of Low Temperature Physics, Charles University, Prague (Czech Republic); Zviagin, Sergei; Cizmar, Erik [Institut Hochfeld-Magnetlabor, Forschungszentrum Dresden-Rossendorf, Dresden (Germany); Ling, Chi Chung; Hsu, Yuk Fan; Xi, Yan Yan; Chen, Xinyi; Djurisic, Aleksandra B. [Department of Physics, University of Hong Kong, Hong Kong (China)

    2009-11-15

    ZnO nanostructures are of special interest for device applications. However, their structural characterization remains an ongoing challenge. This paper reviews recent efforts and latest achievements in this direction. Results comprise PAS in the form of Slow Positron Implantation Spectroscopy (SPIS) and Pulsed Low Energy Positron Lifetime Spectroscopy (PLEPS), Nuclear Reaction Analysis (NRA), Atomic Force Microscopy (AFM), conductive AFM (C-AFM), Nuclear Magnetic Resonance (NMR), Electron Spin Resonance (ESR), Photoluminescence (PL) spectroscopy, and latest theoretical investigations of structure-related and positron properties of selected defects. The fundamental importance of a relationship between fabrication conditions, native defect formation, and resulting optical and electronic properties is demonstrated by getting either inferior (nanorods) or significantly improved (tetrapods) optical properties compared to single crystal samples, depending on the nanostructure fabrication method. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Rotational and Rovibrational Spectroscopy of CH3NC of the Ground and v(4)=1 Vibrational States

    Czech Academy of Sciences Publication Activity Database

    Pracna, Petr; Urban, Jiří; Votava, Ondřej; Meltzerová, Z.; Urban, Š.; Horneman, V. M.; Drouin, B. J.

    2011-01-01

    Roč. 115, č. 6 (2011), s. 1063-1068 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400400706; GA MŠk LC06071 Institutional research plan: CEZ:AV0Z40400503 Keywords : resolution infrared spectroscopy * methyl isocyanide * microwave spectra Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.946, year: 2011

  12. Synthesis, crystal structure, vibrational spectroscopy, optical properties and theoretical studies of a new organic-inorganic hybrid material: [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2.

    Science.gov (United States)

    Ben Ahmed, A; Feki, H; Abid, Y

    2014-12-10

    A new organic-inorganic hybrid material, [((CH3)2NH2)(+)]6·[(BiBr6)(3-)]2, has been synthesized and characterized by X-ray diffraction, FT-IR, Raman spectroscopy and UV-Visible absorption. The studied compound crystallizes in the triclinic system, space group P1¯ with the following parameters: a=8.4749(6)(Å), b=17.1392(12)(Å), c=17.1392(12)(Å), α=117.339(0)°, β=99.487(0)°, γ=99.487(0)° and Z=2. The crystal lattice is composed of a two discrete (BiBr6)(3-) anions surrounded by six ((CH3)2NH2)(+) cations. Complex hydrogen bonding interactions between (BiBr6)(3-) and organic cations from a three-dimensional network. Theoretical calculations were performed using density functional theory (DFT) for studying the molecular structure, vibrational spectra and optical properties of the investigated molecule in the ground state. The full geometry optimization of designed system is performed using DFT method at B3LYP/LanL2DZ level of theory using the Gaussian03. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from FT-IR and Raman spectra are assigned based on the results of the theoretical calculations. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The simulated spectra satisfactorily coincide with the experimental UV-Visible spectrum. The results show good consistent with the experiment and confirm the contribution of metal orbital to the HOMO-LUMO boundary. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Low energy electron diffraction (LEED) and sum frequency generation (SFG) vibrational spectroscopy studies of solid-vacuum, solid-air and solid-liquid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Hoffer, Saskia [Univ. of California, Berkeley, CA (United States)

    2002-01-01

    Electron based surface probing techniques can provide detailed information about surface structure or chemical composition in vacuum environments. The development of new surface techniques has made possible in situ molecular level studies of solid-gas interfaces and more recently, solid-liquid interfaces. The aim of this dissertation is two-fold. First, by using novel sample preparation, Low Energy Electron Diffraction (LEED) and other traditional ultra high vacuum (UHV) techniques are shown to provide new information on the insulator/vacuum interface. The surface structure of the classic insulator NaCl has been determined using these methods. Second, using sum frequency generation (SFG) surface specific vibrational spectroscopy studies were performed on both the biopolymer/air and electrode/electrolyte interfaces. The surface structure and composition of polyetherurethane-silicone copolymers were determined in air using SFG, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). SFG studies of the electrode (platinum, gold and copper)/electrolyte interface were performed as a function of applied potential in an electrochemical cell.

  14. Nanoscale coupling of photons to vibrational excitation of Ag nanoparticle 2D array studied by scanning tunneling microscope light emission spectroscopy.

    Science.gov (United States)

    Katano, Satoshi; Toma, Koji; Toma, Mana; Tamada, Kaoru; Uehara, Yoichi

    2010-11-28

    Scanning tunneling microscope light emission (STM-LE) spectroscopy has been utilized to elucidate the luminescence phenomena of Ag nanoparticles capped with myristate (myristate-capped AgNP) and 2-methyl-1-propanethiolate (C(4)S-capped AgNP) on the dodecanethiol-precovered Au substrate. The STM imaging revealed that myristate-capped AgNPs form an ordered hexagonal array whereas C(4)S-capped AgNPs show imperfect ordering, indicating that a shorter alkyl chain of C(4)S-capped AgNP is not sufficient to form rigid interdigitation. It should be noted that such a nanoparticle ordering affects the luminescence properties of the Ag nanoparticle. We found that the STM-LE is only detected from the Ag nanoparticles forming the two-dimensional superlattice. This indicates that the STM-LE of the Ag nanoparticle is radiated via the collective excitation of the local surface plasmon resonance (LSPR) spread over the Ag nanoparticles. Note that the STM-LE spectra of the Ag nanoparticles exhibit spike-like peaks superimposed on the broad light emission peak. Using Raman spectroscopy, we concluded that the spike-like structure appearing in the STM-LE spectra is associated with the vibrational excitation of the molecule embedded between Ag nanoparticles.

  15. Water Orientation at Ceramide/Water Interfaces Studied by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulation

    KAUST Repository

    Adhikari, Aniruddha

    2016-10-10

    Lipid/water interaction is essential for many biological processes. The water structure at the nonionic lipid interface remains little known, and there is no scope of a priori prediction of water orientation at nonionic interfaces, either. Here, we report our study combining advanced nonlinear spectroscopy and molecular dynamics simulation on the water orientation at the ceramide/water interface. We measured χ spectrum in the OH stretch region of ceramide/isotopically diluted water interface using heterodyne-detected vibrational sum-frequency generation spectroscopy and found that the interfacial water prefers an overall hydrogen-up orientation. Molecular dynamics simulation indicates that this preferred hydrogen-up orientation of water is determined by a delicate balance between hydrogen-up and hydrogen-down orientation induced by lipid-water and intralipid hydrogen bonds. This mechanism also suggests that water orientation at neutral lipid interfaces depends highly on the chemical structure of the lipid headgroup, in contrast to the charged lipid interfaces where the net water orientation is determined solely by the charge of the lipid headgroup.

  16. Phase transition behaviors of the supported DPPC bilayer investigated by sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM).

    Science.gov (United States)

    Wu, Heng-Liang; Tong, Yujin; Peng, Qiling; Li, Na; Ye, Shen

    2016-01-21

    The phase transition behaviors of a supported bilayer of dipalmitoylphosphatidyl-choline (DPPC) have been systematically evaluated by in situ sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM). By using an asymmetric bilayer composed of per-deuterated and per-protonated monolayers, i.e., DPPC-d75/DPPC and a symmetric bilayer of DPPC/DPPC, we were able to probe the molecular structural changes during the phase transition process of the lipid bilayer by SFG spectroscopy. It was found that the DPPC bilayer is sequentially melted from the top (adjacent to the solution) to bottom leaflet (adjacent to the substrate) over a wide temperature range. The conformational ordering of the supported bilayer does not decrease (even slightly increases) during the phase transition process. The conformational defects in the bilayer can be removed after the complete melting process. The phase transition enthalpy for the bottom leaflet was found to be approximately three times greater than that for the top leaflet, indicating a strong interaction of the lipids with the substrate. The present SFG and AFM observations revealed similar temperature dependent profiles. Based on these results, the temperature-induced structural changes in the supported lipid bilayer during its phase transition process are discussed in comparison with previous studies.

  17. Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nemana,S.; Gates, B.

    2006-01-01

    SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

  18. Optical and microstructural characterization of porous silicon using photoluminescence, SEM and positron annihilation spectroscopy

    International Nuclear Information System (INIS)

    Cheung, C K; Nahid, F; Cheng, C C; Beling, C D; Fung, S; Ling, C C; Djurisic, A B; Pramanik, C; Saha, H; Sarkar, C K

    2007-01-01

    We have studied the dependence of porous silicon morphology and porosity on fabrication conditions. N-type (100) silicon wafers with resistivity of 2-5 Ω cm were electrochemically etched at various current densities and anodization times. Surface morphology and the thickness of the samples were examined by scanning electron microscopy (SEM). Detailed information of the porous silicon layer morphology with variation of preparation conditions was obtained by positron annihilation spectroscopy (PAS): the depth-defect profile and open pore interconnectivity on the sample surface has been studied using a slow positron beam. Coincidence Doppler broadening spectroscopy (CDBS) was used to study the chemical environment of the samples. The presence of silicon micropores with diameter varying from 1.37 to 1.51 nm was determined by positron lifetime spectroscopy (PALS). Visible luminescence from the samples was observed, which is considered to be a combination effect of quantum confinement and the effect of Si = O double bond formation near the SiO 2 /Si interface according to the results from photoluminescence (PL) and positron annihilation spectroscopy measurements. The work shows that the study of the positronium formed when a positron is implanted into the porous surface provides valuable information on the pore distribution and open pore interconnectivity, which suggests that positron annihilation spectroscopy is a useful tool in the porous silicon micropores' characterization

  19. Fabrication and Characterization of Planar Spring Based on FR4-PCB for Electrodynamics Vibration Energy Harvesting Application

    Science.gov (United States)

    Sugandi, Gandi; Mambu, Grace A.; Mulyadi, Dadang; Mulyana, Edi

    2017-07-01

    Planar spring as a mechanical resonator is very important in designing an electrodynamic vibration energy harvesting application (EVEH) to generate output power with high efficiency. Generally, component of the mechanical resonator is a cantilever beam that is designed using one cantilever with an inertial mass placed cantilever tip. In this study, a planar spring which has four arms cantilever beam was designed and fabricated using an extra-thin FR4-PCB material with a total thickness of 130 µm. There are four types of planar spring that were designed and fabricated in this research to produce resonant frequencies at about 30, 40, 50 and 60 Hz with 1 mm width cantilever arm and various length of 13.5, 11.2, 9.8 and 8.7 mm, respectively. FR4 resonator is fabricated using technology LASER-cutting in order to obtain results precisely. The resonant frequency generated by the mechanical resonator is characterized using vibrator system with certain acceleration. The resonant frequency of the planar spring was obtained at a frequency where the maximum induced voltage occurs. The resonant frequency generated by each type of planar spring was obtained at 24.81, 34.24, 40.2, and 46.8 Hz with three conditions of acceleration of 0.02, 0.06, and 0,1g (g=9.8 m/s2).

  20. Materials characterization of free volume and void properties by two-dimensional positron annihilation lifetime spectroscopy

    Science.gov (United States)

    Chen, Hongmin; Van Horn, J. David; Jean, Y. C.; Hung, Wei-Song; Lee, Kueir-Rarn

    2013-04-01

    Positron annihilation lifetime spectroscopy (PALS) has been widely used to determine the free volume and void properties in polymeric materials. Recently, a two dimensional positron annihilation lifetime spectroscopy (2DPALS) system has been developed for membrane applications. The system measures the coincident signals between the lifetime and the energy which could separate the 2γ and 3γ annihilations and improve the accuracy in the determination of the free volume and void properties. When 2D-PALS is used in coupling with a variable mono-energy slow positron beam, it could be applied to a variety of material characterization. Results of free volumes and voids properties in a multi-layer polymer membrane characterized using 2D-PALS are presented.

  1. Fourier Transform Infrared (FTIR) Spectroscopy, Ultraviolet Resonance Raman (UVRR) Spectroscopy, and Atomic Force Microscopy (AFM) for Study of the Kinetics of Formation and Structural Characterization of Tau Fibrils.

    Science.gov (United States)

    Ramachandran, Gayathri

    2017-01-01

    Kinetic studies of tau fibril formation in vitro most commonly employ spectroscopic probes such as thioflavinT fluorescence and laser light scattering or negative stain transmission electron microscopy. Here, I describe the use of Fourier transform infrared (FTIR) spectroscopy, ultraviolet resonance Raman (UVRR) spectroscopy, and atomic force microscopy (AFM) as complementary probes for studies of tau aggregation. The sensitivity of vibrational spectroscopic techniques (FTIR and UVRR) to secondary structure content allows for measurement of conformational changes that occur when the intrinsically disordered protein tau transforms into cross-β-core containing fibrils. AFM imaging serves as a gentle probe of structures populated over the time course of tau fibrillization. Together, these assays help further elucidate the structural and mechanistic complexity inherent in tau fibril formation.

  2. Observation of Electronic Excitation Transfer Through Light Harvesting Complex II Using Two-Dimensional Electronic-Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, NHC; Gruenke, NL; Oliver, TAA; Ballottari, M; Bassi, R; Fleming, GR

    2016-10-05

    Light-harvesting complex II (LHCII) serves a central role in light harvesting for oxygenic photosynthesis and is arguably the most important photosynthetic antenna complex. In this article, we present two-dimensional electronic–vibrational (2DEV) spectra of LHCII isolated from spinach, demonstrating the possibility of using this technique to track the transfer of electronic excitation energy between specific pigments within the complex. We assign the spectral bands via comparison with the 2DEV spectra of the isolated chromophores, chlorophyll a and b, and present evidence that excitation energy between the pigments of the complex are observed in these spectra. Lastly, we analyze the essential components of the 2DEV spectra using singular value decomposition, which makes it possible to reveal the relaxation pathways within this complex.

  3. An expanded genetic code for probing the role of electrostatics in enzyme catalysis by vibrational Stark spectroscopy.

    Science.gov (United States)

    Völler, Jan-Stefan; Biava, Hernan; Hildebrandt, Peter; Budisa, Nediljko

    2017-11-01

    To find experimental validation for electrostatic interactions essential for catalytic reactions represents a challenge due to practical limitations in assessing electric fields within protein structures. This review examines the applications of non-canonical amino acids (ncAAs) as genetically encoded probes for studying the role of electrostatic interactions in enzyme catalysis. ncAAs constitute sensitive spectroscopic probes to detect local electric fields by exploiting the vibrational Stark effect (VSE) and thus have the potential to map the protein electrostatics. Mapping the electrostatics in proteins will improve our understanding of natural catalytic processes and, in beyond, will be helpful for biocatalyst engineering. This article is part of a Special Issue entitled "Biochemistry of Synthetic Biology - Recent Developments" Guest Editor: Dr. Ilka Heinemann and Dr. Patrick O'Donoghue. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

    Science.gov (United States)

    Fayer, M D

    2009-01-01

    A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

  5. Characterization by acoustic emission and electrochemical impedance spectroscopy of the cathodic disbonding of Zn coating

    International Nuclear Information System (INIS)

    Amami, Souhail; Lemaitre, Christian; Laksimi, Abdelouahed; Benmedakhene, Salim

    2010-01-01

    Galvanized steel has been tested in a synthetic sea water solution under different cathodic overprotection conditions. The generated hydrogen flux caused the damage of the metal-zinc interface and led to a progressive coating detachment. Scanning electron microscopy, electrochemical impedance spectroscopy and acoustic emission technique were used to characterize the damage chronology under different cathodic potentials. A damage mechanism was proposed and the acoustic signature related to the coating degradation was statistically identified using clustering techniques.

  6. Characterization by acoustic emission and electrochemical impedance spectroscopy of the cathodic disbonding of Zn coating

    Energy Technology Data Exchange (ETDEWEB)

    Amami, Souhail [Universite de Technologie de Compiegne, Departement de Genie Mecanique, Laboratoire Roberval, UMR 6066 du CNRS, B.P. 20529, 60206 Compiegne Cedex (France)], E-mail: souhail.amami@utc.fr; Lemaitre, Christian; Laksimi, Abdelouahed; Benmedakhene, Salim [Universite de Technologie de Compiegne, Departement de Genie Mecanique, Laboratoire Roberval, UMR 6066 du CNRS, B.P. 20529, 60206 Compiegne Cedex (France)

    2010-05-15

    Galvanized steel has been tested in a synthetic sea water solution under different cathodic overprotection conditions. The generated hydrogen flux caused the damage of the metal-zinc interface and led to a progressive coating detachment. Scanning electron microscopy, electrochemical impedance spectroscopy and acoustic emission technique were used to characterize the damage chronology under different cathodic potentials. A damage mechanism was proposed and the acoustic signature related to the coating degradation was statistically identified using clustering techniques.

  7. Surface-enhanced vibrational spectroscopy of B vitamins: what is the effect of SERS-active metals used?

    Science.gov (United States)

    Kokaislová, A; Matějka, P

    2012-05-01

    Surface-enhanced Raman scattering (SERS) spectroscopy and surface-enhanced infrared absorption (SEIRA) spectroscopy are analytical tools suitable for the detection of small amounts of various analytes adsorbed on metal surfaces. During recent years, these two spectroscopic methods have become increasingly important in the investigation of adsorption of biomolecules and pharmaceuticals on nanostructured metal surfaces. In this work, the adsorption of B-group vitamins pyridoxine, nicotinic acid, folic acid and riboflavin at electrochemically prepared gold and silver substrates was investigated using Fourier transform SERS spectroscopy at an excitation wavelength of 1,064 nm. Gold and silver substrates were prepared by cathodic reduction on massive platinum targets. In the case of gold substrates, oxidation-reduction cycles were applied to increase the enhancement factor of the gold surface. The SERS spectra of riboflavin, nicotinic acid, folic acid and pyridoxine adsorbed on silver substrates differ significantly from SERS spectra of these B-group vitamins adsorbed on gold substrates. The analysis of near-infrared-excited SERS spectra reveals that each of B-group vitamin investigated interacts with the gold surface via a different mechanism of adsorption to that with the silver surface. In the case of riboflavin adsorbed on silver substrate, the interpretation of surface-enhanced infrared absorption (SEIRA) spectra was also helpful in investigation of the adsorption mechanism.

  8. Design and Experimental Characterization of a Vibration Energy Harvesting Device for Rotational Systems

    Directory of Open Access Journals (Sweden)

    Lutao Yan

    2013-01-01

    Full Text Available This paper presents a new vibration based electromagnetic power generator to transfer energy from stationary to rotating equipment, which can be a new attempt to substitute slip ring in rotational systems. The natural frequencies and modes are simulated in order to have a maximum and steady power output from the device. Parameters such as piezoelectric disk location and relative motion direction of the magnet are theoretically and experimentally analyzed. The results show that the position that is close to the fixed end of the cantilever and the relative motion along the long side gives higher power output. Moreover, the capability of the energy harvester to extract power from lower energy environment is experimentally validated. The voltage and power output are measured at different excitation frequencies.

  9. Ambient vibration characterization and monitoring of a rock slope close to collapse

    Science.gov (United States)

    Burjánek, Jan; Gischig, Valentin; Moore, Jeffrey R.; Fäh, Donat

    2018-01-01

    We analyse the ambient vibration response of Alpe di Roscioro (AdR), an incipient rock slope failure located above the village Preonzo in southern Switzerland. Following a major failure in May 2012 (volume ˜210 000 m3), the remaining unstable rock mass (˜140 000 m3) remains highly fractured and disrupted, and has been the subject of intensive monitoring. We deployed a small-aperture seismic array at the site shortly after the 2012 failure. The measured seismic response exhibited strong directional amplification (factors up to 35 at 3.5 Hz), higher than previously recorded on rock slopes. The dominant direction of ground motion was found to be parallel to the predominant direction of deformation and perpendicular to open fractures, reflecting subsurface structure of the slope. We then equipped the site with two semi-permanent seismic stations to monitor the seismic response with the goal of identifying changes caused by internal damage that may precede subsequent failure. Although failure has not yet occurred, our data reveal important variations in the seismic response. Amplification factors and resonant frequencies exhibit seasonal trends related (both directly and inversely) to temperature changes and are sensitive to freezing periods (resonant frequencies increase with temperature and during freezing). We attribute these effects to thermal expansion driving microcrack closure, in addition to ice formation, which increase fracture and bulk rock stiffness. We find the site response at AdR is linear over the measured range of weak input motions spanning two orders of magnitude. Our results further develop and refine ambient vibration methods used in rock slope hazard assessment.

  10. A direct pedestrian-structure interaction model to characterize the human induced vibrations on slender footbridges

    Directory of Open Access Journals (Sweden)

    Jiménez-Alonso, J. F.

    2014-12-01

    Full Text Available Although the scientific community had knowledge of the human induced vibration problems in structures since the end of the 19th century, it was not until the occurrence of the vibration phenomenon happened in the Millennium Bridge (London, 2000 that the importance of the problem revealed and a higher level of attention devoted. Despite the large advances achieved in the determination of the human-structure interaction force, one of the main deficiencies of the existing models is the exclusion of the effect of changes in the footbridge dynamic properties due to the presence of pedestrians. In this paper, the formulation of a human-structure interaction model, addresses these limitations, is carried out and its reliability is verified from previously published experimental results.Aunque la comunidad científica tenía conocimiento de los problemas vibratorios inducidos por peatones en estructuras desde finales del siglo xix, no fue hasta la ocurrencia de los eventos vibratorios acontecidos en la pasarela del Milenio (Londres, 2000, cuando la importancia del problema se puso de manifiesto y se le comenzó a dedicar un mayor nivel de atención. A pesar de los grandes avances alcanzados en la caracterización de la fuerza de interacción peatón-estructura una de las principales deficiencias de los modelos existentes es la exclusión del cambio en las propiedades dinámicas de la pasarela por la presencia de peatones. En este artículo, se presenta la formulación de un modelo de interacción peatón-estructura que intenta dar respuesta a dichas limitaciones, y su validación a partir de resultados experimentales previamente publicados por otros autores.

  11. Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

    International Nuclear Information System (INIS)

    Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.

    1981-01-01

    Resonance Raman and electronic absorption spectra are reported for the S 0 and T 1 states of the carotenoids β-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C 50 )-β-carotene, β-apo-8'-carotenal, and ethyl β-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S 0 and T 1 , regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S 0 and T 1 reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T 1 states of carotenoids and in the S 1 states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S 1 lifetime (of the 1 B/sub u/ and/or the 1 A/sub g/* states) of β-carotene in benzene is less than 1 ps

  12. Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand

    Science.gov (United States)

    Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

    2018-01-01

    A series of novel coordination polyurethanes [HTPU-M, where M = Mn(II) 'd5', Ni(II) 'd8', and Zn(II) 'd10'] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, sbnd OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II) > HTPU-Mn(II) > HTPU-Zn(II) > HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants.

  13. Vibrational spectroscopy of NO^+(H_2O)_n: Evidence for the intracluster reaction NO^+(H_2O)_n→H_3O^+(H_2O)_(n-2)(HONO) at n≥4

    OpenAIRE

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-01-01

    Infrared spectra of mass‐selected clusters NO^+(H_2O)_n for n=1 to 5 were recorded from 2700 to 3800 cm^(−1) by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second‐order Møller–Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H_2O...

  14. Adsorption of F2C=CFCl on TiO2 nano-powder: Structures, energetics and vibrational properties from DRIFT spectroscopy and periodic quantum chemical calculations

    International Nuclear Information System (INIS)

    Tasinato, Nicola; Moro, Daniele; Stoppa, Paolo; Pietropolli Charmet, Andrea; Toninello, Piero; Giorgianni, Santi

    2015-01-01

    Graphical abstract: - Highlights: • Adsorption of F 2 C=CFCl on TiO 2 unveiled by DRIFTS and periodic DFT. • Structural, energetic and vibrational properties of F 2 C=CFCl @ anatase (1 0 1). • Binding energies (B3LYP-D2) between −17 and −46 kJ mol −1 depending on the anchor point. • Theory and experiment converge on the CF 2 moiety as the main anchor point. - Abstract: Photodegradation over titanium dioxide (TiO 2 ) is a very appealing technology for removing environmental pollutants from the air, the adsorption interaction being the first step of the whole reaction pathway. In the present work the adsorption of F 2 C=CFCl (chlorotrifluoroethene, halon 1113), a compound used by industry and detected in the atmosphere, on a commercial TiO 2 nano-powder is investigated experimentally by in situ DRIFT spectroscopy and theoretically through periodic ab initio calculations rooted in DFT. The spectra of the adsorbed molecule suggest that the anchoring to the surface mainly takes place through F atoms. Theoretically, five adsorption configurations for the molecule interacting with the anatase (1 0 1) surface are simulated at B3LYP level and for each of them, structures, binding energies and vibrational frequencies are derived. The interplay between theory and experiments shows the coexistence of different adsorption configurations, the foremost ones featuring the interaction of one F atom with a fivefold coordinated Ti 4+ of the surface. These two adsorption models, which mostly differ for the orientation of the adsorbate with respect to the surface, feature a binding energy of −45.6 and −41.0 kJ mol −1 according to dispersion corrected DFT calculations. The favorable adsorption interaction appears as an important requirement toward the application of titanium dioxide technologies for the photocatalytic degradation of halon 1113.

  15. Hydration of Sulphobetaine (SB) and Tetra(ethylene glycol) (EG4)-Terminated Self-Assembled Monolayers Studied by Sum Frequency Generation (SFG) Vibrational Spectroscopy

    Science.gov (United States)

    Stein, M. Jeanette; Weidner, Tobias; McCrea, Keith; Castner, David G.; Ratner, Buddy D.

    2010-01-01

    Sum frequency generation (SFG) vibrational spectroscopy is used to study the surface and the underlying substrate of both homogeneous and mixed self-assembled monolayers (SAMs) of 11-mercaptoundecyl-1-sulphobetainethiol (HS(CH2)11N+(CH3)2(CH2)3SO3−, SB) and 1-mercapto-11-undecyl tetra(ethylene glycol) (HS(CH2)11O(CH2CH2O)4OH, EG4) with an 11-mercapto-1-undecanol (HS(CH2)11OH, MCU) diluent. SFG results on the C–H region of the dry and hydrated SAMs gave an in situ look into the molecular orientation and suggested an approach to maximize signal-to-noise ratio on these difficult to analyze hydrophilic SAMs. Vibrational fingerprint studies in the 3000–3600 cm−1 spectral range for the SAMs exposed serially to air, water, and deuterated water revealed that a layer of tightly-bound structured water was associated with the surface of a non-fouling monolayer but was not present on a hydrophobic N-undecylmercaptan (HS(CH2)10CH3, UnD) control. The percentage of water retained upon submersion in D2O correlated well with the relative amount of protein that was previously shown to absorb onto the monolayers. These results provide evidence supporting the current theory regarding the role of a tightly-bound vicinal water layer in the protein resistance of a non-fouling group. PMID:19639981

  16. Vibrational spectroscopy of hydrated potassium hexauranate for the phase study of the UO3-KCl-H2O system

    International Nuclear Information System (INIS)

    Dothee, Daniel.

    1980-02-01

    In the study of the UO 3 -KCl-H 2 O system, a phase, called C phase, was isolated; it has a radiocrystallogram very close to the hexauranate K 2 U 6 O 19 ,11H 2 O, but K + and Cl - are found in its composition. Links between these two phases are studied and especially structure relationships. Hydrated potassium hexauranate structure was determined previously with a natural crystal. Position of potassium and uranium atoms only are known. As monocrystal preparation is impossible a direct structural study is impossible too. Vibrational spectroscopic analysis was selected for this study. Hexauranate structure is determined and results are extended for the study of the C phase. The hydrate UO 3 .0.8 H 2 O a stable and well defined compound is chosen for the hydrothermal synthesis of the different phases. Four main phases are evidenced: the chloro-uranate Ksub(x)UO 3 Clsub(x) (already known), a hydrated potassium uranate and two phases (one is the C phase) containing chloride ions are intermediaries between the chloro-uranate and the uranate [fr

  17. Conformational analysis and vibrational spectroscopy of a paracetamol analogous: 2-Bromo-N-(2-hydroxy-5-methylphenyl)-2-methylpropanamide

    Science.gov (United States)

    Viana, Rommel B.; Quintero, David E.; Viana, Anderson B.; Moreno-Fuquen, Rodolfo

    2017-11-01

    We conducted an experimental and quantum chemical investigation of the electronic properties and vibrational mode couplings of a structure analogous to a paracetamol (acetaminophen): 2-Bromo-N-(2-hydroxy-5-methylphenyl)-2-methylpropanamide. The spectroscopic and electronic properties were carried out with the PBE1PBE functional, and G3MP2 was used to predict the heat of formation. Among the E/Z stereoisomers, we showed that the energy gap ranged from 3 to 10 kcal mol-1; the relative stability among the regioisomers (involving the different positions of the methyl and hydroxyl groups) exhibited energy differences lower than 5 kcal mol-1. A topological analysis using the Quantum Theory of Atoms in Molecules (QTAIM) was performed to determine the intramolecular hydrogen bonds that govern the configuration changes, and the Natural Bond Orbital method was used to estimate the interplay between the steric and electrostatic interactions that stabilized each isomer. It was also estimated the influence of the population methodology in to predict the atomic charge distribution for the title compound.

  18. DFT approach to (benzylthio)acetic acid: Conformational search, molecular (monomer and dimer) structure, vibrational spectroscopy and some electronic properties

    Science.gov (United States)

    Sienkiewicz-Gromiuk, Justyna

    2018-01-01

    The DFT studies were carried out with the B3LYP method utilizing the 6-31G and 6-311++G(d,p) basis sets depending on whether the aim of calculations was to gain the geometry at equilibrium, or to calculate the optimized molecular structure of (benzylthio)acetic acid (Hbta) in the forms of monomer and dimer. The minimum conformational energy search was followed by the potential energy surface (PES) scan of all rotary bonds existing in the acid molecule. The optimized geometrical monomeric and dimeric structures of the title compound were compared with the experimental structural data in the solid state. The detailed vibrational interpretation of experimental infrared and Raman bands was performed on the basis of theoretically simulated ESFF-scaled wavenumbers calculated for the monomer and dimer structures of Hbta. The electronic characteristics of Hbta is also presented in terms of Mulliken atomic charges, frontier molecular orbitals and global reactivity descriptors. Additionally, the MEP and ESP surfaces were computed to predict coordination sites for potential metal complex formation.

  19. Support effects in catalysis studied by in-situ sum frequency generation vibrational spectroscopy and in-situ x-ray spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Kennedy, Griffin John [Univ. of California, Berkeley, CA (United States)

    2017-04-14

    Here, kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst.

  20. Temperature Dependent Characterization of Terahertz Vibrations of Explosives and Related Threat Materials

    Science.gov (United States)

    2010-12-10

    2 N. Laman , 2 and D. Grischkowsky 2 1Naval Research Laboratory, Electronics Science and Technology Division, Code 6812, Washington, D.C. 20375...spectra of single crystals of high explosives using terahertz time-domain spectroscopy,” J. Phys. Chem. A 109(15), 3501–3505 (2005). 5. N. Laman , S. Sree...Express 16(6), 4094–4105 (2008). 6. J. S. Melinger, N. Laman , and D. Grischkowsky, “The underlying terahertz spectrum of explosive solids,” Appl

  1. Characterization and Simulation of Transient Vibrations Using Band Limited Temporal Moments

    Directory of Open Access Journals (Sweden)

    David O. Smallwood

    1994-01-01

    Full Text Available A method is described to characterize shocks (transient time histories in terms of the Fourier energy spectrum and the temporal moments of the shock passed through a contiguous set of band pass filters. The product model is then used to generate of a random process as simulations that in the mean will have the same energy and moments as the characterization of the transient event.

  2. Spectral and entropic characterizations of Wigner functions: applications to model vibrational systems.

    Science.gov (United States)

    Luzanov, A V

    2008-09-07

    The Wigner function for the pure quantum states is used as an integral kernel of the non-Hermitian operator K, to which the standard singular value decomposition (SVD) is applied. It provides a set of the squared singular values treated as probabilities of the individual phase-space processes, the latter being described by eigenfunctions of KK(+) (for coordinate variables) and K(+)K (for momentum variables). Such a SVD representation is employed to obviate the well-known difficulties in the definition of the phase-space entropy measures in terms of the Wigner function that usually allows negative values. In particular, the new measures of nonclassicality are constructed in the form that automatically satisfies additivity for systems composed of noninteracting parts. Furthermore, the emphasis is given on the geometrical interpretation of the full entropy measure as the effective phase-space volume in the Wigner picture of quantum mechanics. The approach is exemplified by considering some generic vibrational systems. Specifically, for eigenstates of the harmonic oscillator and a superposition of coherent states, the singular value spectrum is evaluated analytically. Numerical computations are given for the nonlinear problems (the Morse and double well oscillators, and the Henon-Heiles system). We also discuss the difficulties in implementation of a similar technique for electronic problems.

  3. Structure and Absolute Configuration of Ginkgolide B Characterized by IR- and VCD Spectroscopy

    DEFF Research Database (Denmark)

    Andersen, Niels Højmark; Christensen, N.J.; Lassen, Peter Rygaard

    2010-01-01

    Experimental and calculated (B3LYP/6-31G(d)) vibrational Circular dichroism (VCD) and IR spectra are compared, illustrating that the structure and absolute configuration of ginkgolide B (GB) may be characterized directly in solution. A conformational search for GB using MacroModel and subsequent...... DFT optimizations (B3LYP/6-31G(d)) provides a structure for the lowest energy conformer which agrees well with the structure determined by X-ray diffraction. In addition, a conformer at all energy of 7 kJ mol(-1) (B3LYP/6-311+G(2d,2p)) with respect to the lowest energy conformer is predicted...

  4. The use of dielectric spectroscopy for the characterization of polymer-induced flocculation of polystyrene particles

    DEFF Research Database (Denmark)

    Christensen, Peter Vittrup; Keiding, Kristian

    2008-01-01

    in dilute suspensions. Thus, techniques usable for flocculation characterization in high-solids suspensions are desirable. This study investigates the use of dielectric spectroscopy to monitor the flocculation of polystyrene particles with a cationic polymer. The frequency-dependent permittivity is modeled......The flocculation of colloidal suspensions is an important unit operation in many industries, as it greatly improves the performance of solid separation processes. The number of available techniques for evaluating flocculation processes on line is limited, and most of these are only functional...... as a decrease in the magnitude of the dielectric dispersion. The use of dielectric spectroscopy is found to be valuable for assessing flocculation processes in high-solids suspensions, as changes in parameters Such as floc size and charge can be detected....

  5. Formation and characterization of varied size germanium nanocrystals by electron microscopy, Raman spectroscopy, and photoluminescence

    DEFF Research Database (Denmark)

    Ou, Haiyan; Ou, Yiyu; Liu, Chuan

    2011-01-01

    Germanium nanocrystals are being extensively examined. Their unique optical properties (brought about by the quantum confinement effect) could potentially be applied in wide areas of nonlinear optics, light emission and solid state memory etc. In this paper, Ge nanocrystals embedded in a SiO2...... matrix were formed by complementary metal-oxide-semiconductor compatible technology, e.g. plasma enhanced chemical vapour deposition and annealing. Different sizes of the Ge nanocrystals were prepared and analyzed by transmission electron microscopy with respect to their size, distribution...... and crystallization. The samples of different size Ge nanocrystals embedded in the SiO2 matrix were characterized by Raman spectroscopy and photoluminescence. Interplayed size and strain effect of Ge nanocystals was demonstrated by Raman spectroscopy after excluding the thermal effect with proper excitation laser...

  6. Application of terahertz spectroscopy for characterization of biologically active organic molecules in natural environment

    Science.gov (United States)

    Karaliūnas, Mindaugas; Jakštas, Vytautas; Nasser, Kinan E.; Venckevičius, Rimvydas; Urbanowicz, Andrzej; Kašalynas, Irmantas; Valušis, Gintaras

    2016-09-01

    In this work, a comparative research of biologically active organic molecules in its natural environment using the terahertz (THz) time domain spectroscopy (TDS) and Fourier transform spectroscopy (FTS) systems is carried out. Absorption coefficient and refractive index of Nicotiana tabacum L. leaves containing nicotine, Cannabis sativa L. leaves containing tetrahydrocannabinol, and Humulu lupulus L. leaves containing α-acids, active organic molecules that obtain in natural environment, were measured in broad frequency range from 0.1 to 13 THz at room temperature. In the spectra of absorption coefficient the features were found to be unique for N. tabacum, C. sativa and H. lupulus. Moreover, those features can be exploited for identification of C. sativa sex and N. tabacum origin. The refractive index can be also used to characterize different species.

  7. Identification of inks and structural characterization of contemporary artistic prints by laser-induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Oujja, M.; Vila, A.; Rebollar, E.; Garcia, J.F.; Castillejo, M.

    2005-01-01

    Identification of the inks used in artistic prints and the order in which different ink layers have been applied on a paper substrate are important factors to complement the classical stylistic aspects for the authentication of this type of objects. Laser-induced breakdown spectroscopy (LIBS) is investigated to determine the chemical composition and structural distribution of the constituent materials of model prints made by applying one or two layers of several blue and black inks on an Arches paper substrate. By using suitable laser excitation conditions, identification of the inks was possible by virtue of emissions from key elements present in their composition. Analysis of successive spectra on the same spot allowed the identification of the order in which the inks were applied on the paper. The results show the potential of laser-induced breakdown spectroscopy for the chemical and structural characterization of artistic prints

  8. Adsorption of 1- and 2-butylimidazoles at the copper/air and steel/air interfaces studied by sum frequency generation vibrational spectroscopy.

    Science.gov (United States)

    Casford, Michael T L; Davies, Paul B

    2012-07-24

    The structure of thin films of 1- and 2-butylimidazoles adsorbed on copper and steel surfaces under air was examined using sum frequency generation (SFG) vibrational spectroscopy in the ppp and ssp polarizations. Additionally, the SFG spectra of both isomers were recorded at 55 °C at the liquid imidazole/air interface for reference. Complementary bulk infrared, reflection-absorption infrared spectroscopy (RAIRS), and Raman spectra of both imidazoles were recorded for assignment purposes. The SFG spectra in the C-H stretching region at the liquid/air interface are dominated by resonances from the methyl end group of the butyl side chain of the imidazoles, indicating that they are aligned parallel or closely parallel to the surface normal. These are also the most prominent features in the SFG spectra on copper and steel. In addition, both the ppp and ssp spectra on copper show resonances from the C-H stretching modes of the imidazole ring for both isomers. The ring C-H resonances are completely absent from the spectra on steel and at the liquid/air interface. The relative intensities of the SFG spectra can be interpreted as showing that, on copper, under air, both butylimidazoles are adsorbed with their butyl side chains perpendicular to the interface and with the ring significantly inclined away from the surface plane and toward the surface normal. The SFG spectra of both imidazoles on steel indicate an orientation where the imidazole rings are parallel or nearly parallel to the surface. The weak C-H resonances from the ring at the liquid/air interface suggest that the tilt angle of the ring from the surface normal at this interface is significantly greater than it is on copper.

  9. Franck-Condon fingerprinting of vibration-tunneling spectra.

    Science.gov (United States)

    Berrios, Eduardo; Sundaradevan, Praveen; Gruebele, Martin

    2013-08-15

    We introduce Franck-Condon fingerprinting as a method for assigning complex vibration-tunneling spectra. The B̃ state of thiophosgene (SCCl2) serves as our prototype. Despite several attempts, assignment of its excitation spectrum has proved difficult because of near-degenerate vibrational frequencies, Fermi resonance between the C-Cl stretching mode and the Cl-C-Cl bending mode, and large tunneling splittings due to the out-of-plane umbrella mode. Hence, the spectrum has never been fitted to an effective Hamiltonian. Our assignment approach replaces precise frequency information with intensity information, eliminating the need for double resonance spectroscopy or combination differences, neither of which have yielded a full assignment thus far. The dispersed fluorescence spectrum of each unknown vibration-tunneling state images its character onto known vibrational progressions in the ground state. By using this Franck-Condon fingerprint, we were able to determine the predominant character of several vibration-tunneling states and assign them; in other cases, the fingerprinting revealed that the states are strongly mixed and cannot be characterized with a simple normal mode assignment. The assigned transitions from vibration-tunneling wave functions that were not too strongly mixed could be fitted within measurement uncertainty by an effective vibration-tunneling Hamiltonian. A fit of all observed vibration-tunneling states will require a full resonance-tunneling Hamiltonian.

  10. Structural, vibrational and electrical characterization of PVA-NH4Br polymer electrolyte system

    International Nuclear Information System (INIS)

    Hema, M.; Selvasekerapandian, S.; Sakunthala, A.; Arunkumar, D.; Nithya, H.

    2008-01-01

    Polymer electrolyte based on PVA doped with different concentrations of NH 4 Br has been prepared by solution casting technique. The complexation of the prepared polymer electrolytes has been studied using X-ray diffraction (XRD) and Fourier transform infra red (FTIR) spectroscopy. The maximum ionic conductivity (5.7x10 -4 S cm -1 ) has been obtained for 25 mol% NH 4 Br-doped PVA polymer electrolyte. The temperature dependence of ionic conductivity of the prepared polymer electrolytes obeys Arrhenius law. The ionic transference number of mobile ions has been estimated by dc polarization method and the results reveal that the conducting species are predominantly ions. The dielectric behavior of the polymer electrolytes has been analyzed using dielectric permittivity and electric modulus spectra

  11. Characterization of modified clinoptilolite

    International Nuclear Information System (INIS)

    Novosad, J.; Jandl, J.; Woollins, J.D.

    1992-01-01

    Samples of clinoptilolite were modified using insoluble hexacyanoferrate from aqueous solution. The modified samples were characterized by elemental analysis, powder X-ray diffraction, solid state NMR and vibrational spectroscopy. The sorption properties of modified clinoptilolite were studied, too. Higher affinity for 137 Cs sorption in comparison with the natural clinoptilolite has been proved. (author) 5 refs.; 3 figs.; 2 tabs

  12. Characterization of tunable light source by optical parametric oscillator for high resolution spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Wu, J. W. [Ewha Womens Univ., Seoul (Korea); Rhee, B. G. [Sejong Univ., Seoul (Korea); Park, S. W. [Yonsei Univ., Seoul (Korea); Noh, J. W. [Inha Univ., Incheon (Korea)

    1998-04-01

    A tunable light source is developed by the optical parametric oscillator, which is very useful for a high resolution spectroscopy. The electronic structure of molecules and atoms can be examined by a proper coherent light source. Optical parametric oscillator provides light sources stable and widely tunable. In this work, the characteristics of the parametric optical generation are examined in the LiNbO{sub 3}. The theoretical analysis as well as the experimental measurement is performed. The pump laser is a second harmonic of Nd:YAG laser, and the parametric gain is measured. The characteristics of singly resonant oscillator and doubly resonant oscillator is studied as a function of temperature. It is found that 1mole% MgO:LiNbO{sub 3} crystal provides the tunability from 0.6{mu}m to 3.0{mu}m wavelength. Both the critical and noncritical phase matching are studied. The optical damage occurring in a congruent LiNbO{sub 3} crystal was not observed in 1mole% MgO:LiNbO{sub 3} crystal, opening a possibility for a high power optical parametric oscillation generation. The current work can be extended to an experiment employing the fundamental Nd:YAG as pump to provide a coherent light source for the study of molecular vibrations. 28 refs., 14 figs., 3 tabs. (Author)

  13. IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Ni, Yicun; Skinner, J. L. [Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 (United States)

    2015-07-07

    Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm{sup −1} and a positive band centered at 1670 cm{sup −1}. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

  14. Optical and vibrational spectroscopy of Ba0.85Ca0.15Zr0.1Ti0.9O3 modified lithium borate glass ceramics

    Science.gov (United States)

    Viswanath, Pamarti; Prashanth, Sadhu Sai Pavan; Molli, Muralikrishna; Wicram, Jaschin Prem; Sai Muthukumar, V.

    2018-04-01

    Glass ceramics are excellent replacement for single crystalline materials which are expensive and difficult to fabricate. In this context, we have attempted to fabricate glass nanocomposites comprising of Lithium Borate glass matrix embedded with lead free ferroelectric Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT). Both of these functional materials are known to exhibit excellent ferroelectric behavior and are currently explored for various device applications. We have prepared these novel glass nanocomposite using melt-quenching techniquein various chemical composition involving different molar ratio. x(Ba0.85Ca0.15Zr0.1Ti0.9O3)-(1-x)(Li2O.2B2O3) where (x=0.1,0.2,0.3,0.4). The as-quenched samples exhibited amorphous nature as revealed by X-ray Diffraction studies. With the increase in BCZT content we have observed significant alteration in optical bandgap and Urbach energy. The tailoring of optical properties by tuning the structure was probed by Raman vibrational spectroscopy which confirmed the dominant role played by BCZT as a network modifier in these borate glasses. Concomitantly, these glass nanocomposites were found to be excellent UV absorbers.

  15. IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively

    Science.gov (United States)

    Ni, Yicun; Skinner, J. L.

    2015-07-01

    Vibrational spectroscopy of the water bending mode has been investigated experimentally to study the structure of water in condensed phases. In the present work, we calculate the theoretical infrared (IR) and sum-frequency generation (SFG) spectra of the HOH bend in liquid water and at the water liquid/vapor interface using a mixed quantum/classical approach. Classical molecular dynamics simulation is performed by using a recently developed water model that explicitly includes three-body interactions and yields a better description of the water surface. Ab-initio-based transition frequency, dipole, polarizability, and intermolecular coupling maps are developed for the spectral calculations. The calculated IR and SFG spectra show good agreement with the experimental measurements. In the theoretical imaginary part of the SFG susceptibility for the water liquid/vapor interface, we find two features: a negative band centered at 1615 cm-1 and a positive band centered at 1670 cm-1. We analyze this spectrum in terms of the contributions from molecules in different hydrogen-bond classes to the SFG spectral density and also compare to SFG results for the OH stretch. SFG of the water bending mode provides a complementary picture of the heterogeneous hydrogen-bond configurations at the water surface.

  16. Hydrogenation of the alpha,beta-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Kliewer, C.J.; Somorjai, G.A.

    2008-11-26

    Sum-frequency generation vibrational spectroscopy (SFG-VS) and kinetic measurements using gas chromatography have been used to study the surface reaction intermediates during the hydrogenation of three {alpha},{beta}-unsaturated aldehydes, acrolein, crotonaldehyde, and prenal, over Pt(111) at Torr pressures (1 Torr aldehyde, 100 Torr hydrogen) in the temperature range of 295K to 415K. SFG-VS data showed that acrolein has mixed adsorption species of {eta}{sub 2}-di-{sigma}(CC)-trans, {eta}{sub 2}-di-{sigma}(CC)-cis as well as highly coordinated {eta}{sub 3} or {eta}{sub 4} species. Crotonaldehyde adsorbed to Pt(111) as {eta}{sub 2} surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the {eta}{sub 2} adsorption species, and became more highly coordinated as the temperature was raised to 415K, in agreement with its enhanced C=O hydrogenation. The effect of catalyst surface structure was clarified by carrying out the hydrogenation of crotonaldehyde over both Pt(111) and Pt(100) single crystals while acquiring the SFG-VS spectra in situ. Both the kinetics and SFG-VS showed little structure sensitivity. Pt(100) generated more decarbonylation 'cracking' product while Pt(111) had a higher selectivity for the formation of the desired unsaturated alcohol, crotylalcohol.

  17. Characterization of the ground state dynamics of proteorhodopsin by NMR and optical spectroscopies

    International Nuclear Information System (INIS)

    Stehle, Jochen; Scholz, Frank; Löhr, Frank; Reckel, Sina; Roos, Christian; Blum, Michaela; Braun, Markus; Glaubitz, Clemens; Dötsch, Volker; Wachtveitl, Josef; Schwalbe, Harald

    2012-01-01

    We characterized the dynamics of proteorhodopsin (PR), solubilized in diC7PC, a detergent micelle, by liquid-state NMR spectroscopy at T = 323 K. Insights into the dynamics of PR at different time scales could be obtained and dynamic hot spots could be identified at distinct, functionally relevant regions of the protein, including the BC loop, the EF loop, the N-terminal part of helix F and the C-terminal part of helix G. We further characterize the dependence of the photocycle on different detergents (n-Dodecyl β-D-maltoside DDM; 1,2-diheptanoyl-sn-glycero-3-phosphocholine diC7PC) by ultrafast time-resolved UV/VIS spectroscopy. While the photocycle intermediates of PR in diC7PC and DDM exhibit highly similar spectral characteristics, significant changes in the population of these intermediates are observed. In-situ NMR experiments have been applied to characterize structural changes during the photocycle. Light-induced chemical shift changes detected during the photocycle in diC7PC are very small, in line with the changes in the population of intermediates in the photocycle of proteorhodopsin in diC7PC, where the late O-intermediate populated in DDM is missing and the population is shifted towards an equilibrium of intermediates states (M, N, O) without accumulation of a single populated intermediate.

  18. Synthesizing and Characterizing Graphene via Raman Spectroscopy: An Upper-Level Undergraduate Experiment That Exposes Students to Raman Spectroscopy and a 2D Nanomaterial

    Science.gov (United States)

    Parobek, David; Shenoy, Ganesh; Zhou, Feng; Peng, Zhenbo; Ward, Michelle; Liu, Haitao

    2016-01-01

    In this upper-level undergraduate experiment, students utilize micro-Raman spectroscopy to characterize graphene prepared by mechanical exfoliation and chemical vapor deposition (CVD). The mechanically exfoliated samples are prepared by the students while CVD graphene can be purchased or obtained through outside sources. Owing to the intense Raman…

  19. Preliminary study for the reliability Assurance on results and procedure of the out-pile mechanical characterization test for a fuel assembly; Lateral Vibration Test (I)

    International Nuclear Information System (INIS)

    Lee, Kang Hee; Yoon, Kyung Hee; Kim, Hyung Kyu

    2007-01-01

    The reliability assurance with respect to the test procedure and results of the out-pile mechanical performance test for the nuclear fuel assembly is an essential task to assure the test quality and to get a permission for fuel loading into the commercial reactor core. For the case of vibration test, proper management and appropriate calibration of instruments and devices used in the test, various efforts to minimize the possible error during the test and signal acquisition process are needed. Additionally, the deep understanding both of the theoretical assumption and simplification for the signal processing/modal analysis and of the functions of the devices used in the test were highly required. In this study, the overall procedure and result of lateral vibration test were assembly's mechanical characterization were briefly introduced. A series of measures to assure and improve the reliability of the vibration test were discussed

  20. Preliminary study for the reliability Assurance on results and procedure of the out-pile mechanical characterization test for a fuel assembly; Lateral Vibration Test (I)

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kang Hee; Yoon, Kyung Hee; Kim, Hyung Kyu [KAERI, Daejeon (Korea, Republic of)

    2007-07-01

    The reliability assurance with respect to the test procedure and results of the out-pile mechanical performance test for the nuclear fuel assembly is an essential task to assure the test quality and to get a permission for fuel loading into the commercial reactor core. For the case of vibration test, proper management and appropriate calibration of instruments and devices used in the test, various efforts to minimize the possible error during the test and signal acquisition process are needed. Additionally, the deep understanding both of the theoretical assumption and simplification for the signal processing/modal analysis and of the functions of the devices used in the test were highly required. In this study, the overall procedure and result of lateral vibration test were assembly's mechanical characterization were briefly introduced. A series of measures to assure and improve the reliability of the vibration test were discussed.

  1. Structural, electronic and vibrational properties of LaF3 according to density functional theory and Raman spectroscopy

    Science.gov (United States)

    Oreshonkov, A. S.; Roginskii, E. M.; Krylov, A. S.; Ershov, A. A.; Voronov, V. N.

    2018-06-01

    Crystal structure of LaF3 single crystal is refined in tysonite-type trigonal unit cell P c1 using density functional theory calculations and Raman spectroscopy. It is shown that trigonal structure with P c1 space group is more energy-efficient than hexagonal structure with space group P63 cm. Simulated Raman spectra obtained using LDA approximation is in much better agreement with experimental data than that obtained with PBE and PBEsol functionals of GGA. The calculated frequency value of silent mode B 2 in case of hexagonal structure P63 cm was found to be imaginary (unstable mode), thus the energy surface obtains negative curvature with respect to the corresponding normal coordinates of the mode which leads to instability of the hexagonal structure in harmonic approximation. The A 1g line at 214 cm‑1 in Raman spectra of LaF3 related to the translation of F2 ions along c axis can be connected with F2 ionic conductivity.

  2. Vibrational spectroscopy and analytical electron microscopy studies of Fe-V-O and In-V-O thin films

    CERN Document Server

    Vuk, A S; Drazic, G; Colomban, P

    2002-01-01

    Orthovanadate (M sup 3 sup + VO sub 4; M= Fe, In) and vanadate (Fe sub 2 V sub 4 O sub 1 sub 3) thin films were prepared using sol-gel synthesis and dip coating deposition. Using analytical electron microscopy (AEM), the chemical composition and the degree of crystallization of the phases present in the thin Fe-V-O films were investigated. TEM samples were prepared in both orientations: parallel (plan view) and perpendicular (cross section) to the substrate. In the first stages of crystallization, when the particle sizes were in the nanometer range, the classical identification of phases using electron diffraction was not possible. Instead of measuring d values, experimentally selected area electron diffraction (SAED) patterns were compared to calculated (simulated) patterns in order to determine the phase composition. The problems of evaluating the ratio of amorphous and crystalline phases in thin films are reported. Results of TEM and XRD as well as IR and Raman spectroscopy showed that the films made at lo...

  3. Characterization of the major nutritional components of Caryocar brasiliense fruit pulp by NMR spectroscopy

    International Nuclear Information System (INIS)

    Miranda-Vilela, Ana Luisa; Grisolia, Cesar Koppe; Resck, Ines Sabioni; Mendonca, Marcio Antonio

    2009-01-01

    Pequi (Caryocar brasiliense Camb.), a typical fruit of Brazilian Cerrado, is well known in regional cookery and used in folk medicine to treat various illnesses. Mass spectrometry and chromatographic methods have identified the organic composition of pequi fruit pulp; however, NMR spectroscopy is used for the first time to characterize the nutritional components of organic and aqueous-ethanolic extracts. This spectroscopic technique determined the triacylglycerols in the pequi organic fraction, which is constituted mainly by oleate and palmitate esters, and detected the carbohydrate mixtures as the major components of aqueous and ethanolic fractions, respectively. In this study, presence of phenolic compounds was only evidenced in the ethanolic fraction. (author)

  4. Characterization of the major nutritional components of Caryocar brasiliense fruit pulp by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Miranda-Vilela, Ana Luisa; Grisolia, Cesar Koppe [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Ciencias Biologicas. Dept. de Genetica e Morfologia; Resck, Ines Sabioni; Mendonca, Marcio Antonio [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica

    2009-07-01

    Pequi (Caryocar brasiliense Camb.), a typical fruit of Brazilian Cerrado, is well known in regional cookery and used in folk medicine to treat various illnesses. Mass spectrometry and chromatographic methods have identified the organic composition of pequi fruit pulp; however, NMR spectroscopy is used for the first time to characterize the nutritional components of organic and aqueous-ethanolic extracts. This spectroscopic technique determined the triacylglycerols in the pequi organic fraction, which is constituted mainly by oleate and palmitate esters, and detected the carbohydrate mixtures as the major components of aqueous and ethanolic fractions, respectively. In this study, presence of phenolic compounds was only evidenced in the ethanolic fraction. (author)

  5. Femtosecond nonlinear spectroscopy at surfaces: Second-harmonic probing of hole burning at the Si(111)7x7 surface and Fourier-transform sum-frequency vibrational spectroscopy

    International Nuclear Information System (INIS)

    McGuire, John Andrew

    2004-01-01

    The high temporal resolution and broad bandwidth of a femtosecond laser system are exploited in a pair of nonlinear optical studies of surfaces. The dephasing dynamics of resonances associated with the adatom dangling bonds of the Si(111)7 x 7 surface are explored by transient second-harmonic hole burning, a process that can be described as a fourth-order nonlinear optical process. Spectral holes produced by a 100 fs pump pulse at about 800 nm are probed by the second harmonic signal of a 100 fs pulse tunable around 800 nm. The measured spectral holes yield homogeneous dephasing times of a few tens of femtoseconds. Fits with a Lorentzian spectral hole centered at zero probe detuning show a linear dependence of the hole width on pump fluence, which suggests that charge carrier-carrier scattering dominates the dephasing dynamics at the measured excitation densities. Extrapolation of the deduced homogeneous dephasing times to zero excitation density yields an intrinsic dephasing time of ∼ 70 fs. The presence of a secondary spectral hole indicates that scattering of the surface electrons with surface optical phonons at 570 cm -1 occurs within the first 200 fs after excitation. The broad bandwidth of femtosecond IR pulses is used to perform IR-visible sum frequency vibrational spectroscopy. By implementing a Fourier-transform technique, we demonstrate the ability to obtain sub-laser-bandwidth spectral resolution. FT-SFG yields a greater signal when implemented with a stretched visible pulse than with a femtosecond visible pulse. However, when compared with multichannel spectroscopy using a femtosecond IR pulse but a narrowband visible pulse, Fourier-transform SFG is found to have an inferior signal-to-noise ratio. A mathematical analysis of the signal-to-noise ratio illustrates the constraints on the Fourier-transform approach

  6. Femtosecond nonlinear spectroscopy at surfaces: Second-harmonic probing of hole burning at the Si(111)7x7 surface and fourier-transform sum-frequency vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    McGuire, John Andrew [Univ. of California, Berkeley, CA (United States)

    2004-11-24

    The high temporal resolution and broad bandwidth of a femtosecond laser system are exploited in a pair of nonlinear optical studies of surfaces. The dephasing dynamics of resonances associated with the adatom dangling bonds of the Si(111)7 x 7 surface are explored by transient second-harmonic hole burning, a process that can be described as a fourth-order nonlinear optical process. Spectral holes produced by a 100 fs pump pulse at about 800 nm are probed by the second harmonic signal of a 100 fs pulse tunable around 800 nm. The measured spectral holes yield homogeneous dephasing times of a few tens of femtoseconds. Fits with a Lorentzian spectral hole centered at zero probe detuning show a linear dependence of the hole width on pump fluence, which suggests that charge carrier-carrier scattering dominates the dephasing dynamics at the measured excitation densities. Extrapolation of the deduced homogeneous dephasing times to zero excitation density yields an intrinsic dephasing time of {approx} 70 fs. The presence of a secondary spectral hole indicates that scattering of the surface electrons with surface optical phonons at 570 cm-1 occurs within the first 200 fs after excitation. The broad bandwidth of femtosecond IR pulses is used to perform IR-visible sum frequency vibrational spectroscopy. By implementing a Fourier-transform technique, we demonstrate the ability to obtain sub-laser-bandwidth spectral resolution. FT-SFG yields a greater signal when implemented with a stretched visible pulse than with a femtosecond visible pulse. However, when compared with multichannel spectroscopy using a femtosecond IR pulse but a narrowband visible pulse, Fourier-transform SFG is found to have an inferior signal-to-noise ratio. A mathematical analysis of the signal-to-noise ratio illustrates the constraints on the Fourier-transform approach.

  7. Characterization of Colloidal Quantum Dot Ligand Exchange by X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Atewologun, Ayomide; Ge, Wangyao; Stiff-Roberts, Adrienne D.

    2013-05-01

    Colloidal quantum dots (CQDs) are chemically synthesized semiconductor nanoparticles with size-dependent wavelength tunability. Chemical synthesis of CQDs involves the attachment of long organic surface ligands to prevent aggregation; however, these ligands also impede charge transport. Therefore, it is beneficial to exchange longer surface ligands for shorter ones for optoelectronic devices. Typical characterization techniques used to analyze surface ligand exchange include Fourier-transform infrared spectroscopy, x-ray diffraction, transmission electron microscopy, and nuclear magnetic resonance spectroscopy, yet these techniques do not provide a simultaneously direct, quantitative, and sensitive method for evaluating surface ligands on CQDs. In contrast, x-ray photoelectron spectroscopy (XPS) can provide nanoscale sensitivity for quantitative analysis of CQD surface ligand exchange. A unique aspect of this work is that a fingerprint is identified for shorter surface ligands by resolving the regional XPS spectrum corresponding to different types of carbon bonds. In addition, a deposition technique known as resonant infrared matrix-assisted pulsed laser evaporation is used to improve the CQD film uniformity such that stronger XPS signals are obtained, enabling more accurate analysis of the ligand exchange process.

  8. Electrochemical Characterization and Degradation Analysis of Large SOFC Stacks by Impedance Spectroscopy

    DEFF Research Database (Denmark)

    Mosbæk, Rasmus Rode; Hjelm, Johan; Barfod, R.

    2013-01-01

    As solid oxide fuel cell (SOFC) technology is moving closer to a commercial break through, lifetime limiting factors, and methods to measure the “state-of-health” of operating cells and stacks are becoming of increasing interest. This requires application of advanced methods for detailed...... electrochemical characterization during operation. An experimental stack with low ohmic resistance from Topsoe Fuel Cell A/S was characterized in detail using electrochemical impedance spectroscopy (EIS). An investigation of the optimal geometrical placement of the current feeds and voltage probes was carried out...... with hydrogen as fuel with 52% fuel utilization and constant current load (0.2 A cm–2) at 750 °C. Stack interconnects were coated with six different coatings to prevent chromium poisoning on the cathode side. Four repeating units (RUs) with different coatings were selected for detailed impedance analysis. EIS...

  9. Characterization of organic photovoltaic devices using femtosecond laser induced breakdown spectroscopy

    Science.gov (United States)

    Banerjee, S. P.; Sarnet, Thierry; Siozos, Panayiotis; Loulakis, Michalis; Anglos, Demetrios; Sentis, Marc

    2017-10-01

    The potential of laser induced breakdown spectroscopy (LIBS) as a non-contact probe, for characterizing organic photovoltaic devices during selective laser scribing, was investigated. Samples from organic solar cells were studied, which consisted of several layers of materials including a top electrode (Al, Mg or Mo), organic layer, bottom electrode (indium tin oxide), silicon nitride barrier layer and substrate layer situated from the top consecutively. The thickness of individual layers varies from 115 to 250 nm. LIBS measurements were performed by use of a 40 femtosecond Ti:Sapphire laser operated at very low pulse energy (solar cell structure, demonstrating the potential of LIBS for fast, non-contact characterization of organic photovoltaic coatings.

  10. Synthesis, characterization and behaviour to gamma radiation of the bis-L-alaninato-copper (II)

    International Nuclear Information System (INIS)

    Passos, B.F.T.

    1985-01-01

    The behaviour of coordinated compound obtained from the copper (II) and the L-(+)- alanine to gamma radiation was determined. A study of synthesis and characterization of this complex was made with elementary analysis, ultraviolet and visible electronic spectroscopy, infrared vibrational spectroscopy, proton magnetic resonance spectroscopy and thermo-gravimetric analysis. (C.G.C.)

  11. X-ray photoelectron spectroscopy characterization of the ω phase in water quenched Ti-5553 alloy

    International Nuclear Information System (INIS)

    Qin, Dongyang; Lu, Yafeng; Zhang, Kong; Liu, Qian; Zhou, Lian

    2012-01-01

    X-ray photoelectron spectroscopy was used to investigate the ω phase in water quenched Ti-5553 alloy with a nominal composition of Ti–5Al–5V–5Mo–3Cr (wt.%), and the ω and the β phase were distinguished by deconvoluting the XPS spectra of Al2p, V2p and Cr2p core level regions. In addition, it is found that the binding energy of core level electron of alloying elements shifts comparing with that of pure metals, and the fact was interpreted by charge redistribution model. X-ray photoelectron spectroscopy technique could be used to characterize the nano-scale ω phase in β alloys. - Highlights: ► We characterize the ω phase in Ti-5553 alloy by XPS. ► Binding energy of Al2p, V2p and Cr2p electron are different in the ω and β phase. ► Structural difference leads to the binding energy gap.

  12. FTIR spectroscopy and X-ray powder diffraction characterization of microcrystalline cellulose obtained from alfa fibers

    Directory of Open Access Journals (Sweden)

    Trache D.

    2013-07-01

    Full Text Available Many cereal straws have been used as raw materials for the preparation of microcrystalline cellulose (MCC. These raw materials were gradually replaced with wood products; nevertheless about 10% of the world overall pulp production is obtained from non-wood raw material. The main interest in pulp made from straw is that it provides excellent fibres for different industries with special properties, and that it is the major available source of fibrous raw material in some geographical areas. The aim of the present work was to characterize microcrystalline cellulose prepared from alfa fibers using the hydrolysis process. The products obtained are characterized with FTIR spectroscopy and X-ray powder diffraction. As a result, FTIR spectroscopy is an appropriate technique for studying changes occurred by any chemical treatment. The spectrum of alfa grass stems shows the presence of lignin and hemicelluloses. However, the cellulose spectrum indicates that the extraction of lignin and hemicellulose was effective. The X-ray analysis indicates that the microcrystalline cellulose is more crystalline than the source material.

  13. Characterization of hard coatings produced by laser cladding using laser-induced breakdown spectroscopy technique

    Energy Technology Data Exchange (ETDEWEB)

    Varela, J.A.; Amado, J.M.; Tobar, M.J.; Mateo, M.P.; Yañez, A.; Nicolas, G., E-mail: gines@udc.es

    2015-05-01

    Highlights: • Chemical mapping and profiling by laser-induced breakdown spectroscopy (LIBS) of coatings produced by laser cladding. • Production of laser clads using tungsten carbide (WC) and nickel based matrix (NiCrBSi) powders. • Calibration by LIBS of hardfacing alloys with different WC concentrations. - Abstract: Protective coatings with a high abrasive wear resistance can be obtained from powders by laser cladding technique, in order to extend the service life of some industrial components. In this work, laser clad layers of self-fluxing NiCrBSi alloy powder mixed with WC powder have been produced on stainless steel substrates of austenitic type (AISI 304) in a first step and then chemically characterized by laser-induced breakdown spectroscopy (LIBS) technique. With the suitable laser processing parameters (mainly output power, beam scan speed and flow rate) and powders mixture proportions between WC ceramics and NiCrBSi alloys, dense pore free layers have been obtained on single tracks and on large areas with overlapped tracks. The results achieved by LIBS technique and applied for the first time to the analysis of laser clads provided the chemical composition of the tungsten carbides in metal alloy matrix. Different measurement modes (multiple point analyses, depth profiles and chemical maps) have been employed, demonstrating the usefulness of LIBS technique for the characterization of laser clads based on hardfacing alloys. The behavior of hardness can be explained by LIBS maps which evidenced the partial dilution of some WC spheres in the coating.

  14. Chlorococcalean microalgae Ankistrodesmus convolutes biodiesel characterization with Fourier transform-infrared spectroscopy and gas chromatography mass spectroscopy techniques

    Directory of Open Access Journals (Sweden)

    Swati SONAWANE

    2015-12-01

    Full Text Available The Chlorococcalean microalgae Ankistrodesmus convolutes was found in fresh water Godawari reservoir, Ahmednagar district of Maharashtra State, India. Microalgae are modern biomass for the production of liquid biofuel due to its high solar cultivation efficiency. The collection, harvesting and drying processes were play vital role in converting algal biomass into energy liquid fuel. The oil extraction was the important step for the biodiesel synthesis. The fatty acid methyl ester (FAME synthesis was carried through base catalyzed transesterification method. The product was analyzed by using the hyphened techniques like Fourier Transform-Infrared spectroscopy (FT-IR and Gas Chromatography Mass Spectroscopy (GCMS. FT-IR Spectroscopy was results the ester as functional group of obtained product while the Gas Chromatography Mass Spectroscopy was results the six type of fatty acid methyl ester with different concentration. Ankistrodesmus convolutes biodiesel consist of 46.5% saturated and 49.14% unsaturated FAME.

  15. Characterization of Maize Grains with Different Pigmentation Investigated by Photoacoustic Spectroscopy

    Science.gov (United States)

    Rico Molina, R.; Hernández Aguilar, C.; Dominguez Pacheco, A.; Cruz-Orea, A.; López Bonilla, J. L.

    2014-10-01

    A knowledge of grains' optical parameters is of great relevance in the maize grain technology practice. Such parameters provide information about its absorption and reflectance, which in turn is related to its color. In the dough and tortilla industries, it is important to characterize this attribute of the corn kernel, as it is one of the attributes that directly affects the quality of the food product. Thus, it is important to have techniques that contribute to the characterization of this raw material. It is traditionally characterized by conventional methods, which usually destroy the grain and involve a laborious preparation of material plus they are expensive. The objective of this study was to determine the optical absorption coefficient for maize grains ( Zea mays L.) with different pigmentations by means of photoacoustic spectroscopy (PAS). The genotype A had bluish coloration and genotype B had yellowish coloration. In addition, the photoacoustic signal obtained by two methods was analyzed mathematically: the standard deviation and the first derivative; both results were compared (Fig. 1). In combination with mathematical analysis, PAS may be considered as a potential diagnostic tool for the characterization of the grains. [Figure not available: see fulltext.

  16. Characterization system for Germanium detectors dedicated to gamma spectroscopy applied to nuclear waste

    Energy Technology Data Exchange (ETDEWEB)

    Roccaz, J.; Portella, C.; Saurel, N. [CEA, DAM, VALDUC, F-21120 Is-sur-Tille (France)

    2009-07-01

    CEA-Valduc produces some radioactive waste (mainly alpha emitters). Legislation requires producers to sort their waste by activity and type of isotopes, and to package them in order to forward them to the appropriate reprocessing or storage facility. Our lab LMDE (laboratory for measurements on nuclear wastes and valuation) is in charge of the characterization of the majority of waste produced by CEA-Valduc. Among non-destructive methods to characterize a radioactive object, gamma-spectroscopy is one of the most efficient. We present to this conference the method we use to characterize nuclear waste and the system we developed to characterize our germanium detectors. The goal of this system is to obtain reliable numerical models of our detectors and calculate their efficiency curves. Measurements are necessary to checks models and improve them. These measurements are made on a bench using pinpoint sources ({sup 133}Ba, {sup 152}Eu) from 60 keV to 1500 keV, with distances from 'on contact' to a few meters from the diode and variable angles between the source and the detector axis. We have demonstrated that we are able to obtain efficiency curves

  17. Parallel β-sheet vibrational couplings revealed by 2D IR spectroscopy of an isotopically labeled macrocycle: quantitative benchmark for the interpretation of amyloid and protein infrared spectra.

    Science.gov (United States)

    Woys, Ann Marie; Almeida, Aaron M; Wang, Lu; Chiu, Chi-Cheng; McGovern, Michael; de Pablo, Juan J; Skinner, James L; Gellman, Samuel H; Zanni, Martin T

    2012-11-21

    Infrared spectroscopy is playing an important role in the elucidation of amyloid fiber formation, but the coupling models that link spectra to structure are not well tested for parallel β-sheets. Using a synthetic macrocycle that enforces a two stranded parallel β-sheet conformation, we measured the lifetimes and frequency for six combinations of doubly (13)C═(18)O labeled amide I modes using 2D IR spectroscopy. The average vibrational lifetime of the isotope labeled residues was 550 fs. The frequencies of the labels ranged from 1585 to 1595 cm(-1), with the largest frequency shift occurring for in-register amino acids. The 2D IR spectra of the coupled isotope labels were calculated from molecular dynamics simulations of a series of macrocycle structures generated from replica exchange dynamics to fully sample the conformational distribution. The models used to simulate the spectra include through-space coupling, through-bond coupling, and local frequency shifts caused by environment electrostatics and hydrogen bonding. The calculated spectra predict the line widths and frequencies nearly quantitatively. Historically, the characteristic features of β-sheet infrared spectra have been attributed to through-space couplings such as transition dipole coupling. We find that frequency shifts of the local carbonyl groups due to nearest neighbor couplings and environmental factors are more important, while the through-space couplings dictate the spectral intensities. As a result, the characteristic absorption spectra empirically used for decades to assign parallel β-sheet secondary structure arises because of a redistribution of oscillator strength, but the through-space couplings do not themselves dramatically alter the frequency distribution of eigenstates much more than already exists in random coil structures. Moreover, solvent exposed residues have amide I bands with >20 cm(-1) line width. Narrower line widths indicate that the amide I backbone is solvent

  18. Characterization of gaseous species in scanning atmospheric rf plasma with transmission infrared spectroscopy

    International Nuclear Information System (INIS)

    Kim, Seong H.; Kim, Jeong Hoon; Kang, Bang-Kwon

    2008-01-01

    A scanning atmospheric radio-frequency (rf) plasma was analyzed with transmission infrared (IR) spectroscopy. The IR analyses were made for the plasmas used for hydrophobic coating deposition and superhydrophobic coating deposition processes. Since the rf plasma was generated in a small open space with a high gas flow rate in ambient air, the density of gas-phase molecules was very high and the plasma-generated reactive species seemed to undergo various reactions in the gas phase. So, the transmission IR spectra of the scanning atmospheric rf plasma were dominated by gas-phase reaction products, rather than plasma-generated intermediate species. In the CH 4 /He plasma used for hydrophobic coating deposition, C 2 H 6 , C 2 H 2 , and a small amount of C 2 H 4 as well as CO were detected in transmission IR. The intensities of these peaks increased as the rf power increased. The CO formation is due to the activation of oxygen and water in the air. In the CF 4 /H 2 /He plasma used for deposition of superhydrophobic coatings, C 2 F 6 , CF 3 H, COF 2 , and HF were mainly detected. When the H 2 /CF 4 ratio was ∼0.5, the consumption of CF 4 was the highest. As the H 2 /CF 4 ratio increased higher, the C 2 F 6 production was suppressed while the CF 3 H peak grew and the formation of CH 4 were detected. In both CH 4 /He and CF 4 /H 2 /He plasma systems, the undissociated feed gas molecules seem to be highly excited vibrationally and rotationally. The information on plasma-generated reactive species and their reactions was deduced from the distribution of these gas-phase reaction products

  19. Modern spectroscopy

    CERN Document Server

    Hollas, J Michael

    2013-01-01

    The latest edition of this highly acclaimed title introduces the reader to a wide range of spectroscopies, and includes both the background theory and applications to structure determination and chemical analysis.  It covers rotational, vibrational, electronic, photoelectron and Auger spectroscopy, as well as EXAFs and the theory of lasers and laser spectroscopy. A  revised and updated edition of a successful, clearly written book Includes the latest developments in modern laser techniques, such as cavity ring-down spectroscopy and femtosecond lasers Provides numerous worked examples, calculations and questions at the end of chapters.

  20. Characterization of lipid oxidation process of beef during repeated freeze-thaw by electron spin resonance technology and Raman spectroscopy.

    Science.gov (United States)

    Chen, Qingmin; Xie, Yunfei; Xi, Jinzhong; Guo, Yahui; Qian, He; Cheng, Yuliang; Chen, Yi; Yao, Weirong

    2018-03-15

    In this study, electron spin resonance (ESR) and Raman spectroscopy were applied to characterize lipid oxidation of beef during repeated freeze-thaw (RFT). Besides the conventional indexes including peroxide values (PV), thiobarbituric acid-reactive substances (TBARS) and acid values (AV) were evaluated, the radical and molecular structure changes were also measured by ESR and Raman spectroscopy. The results showed that PV, TBARS and AV were increased (PRaman intensity of ν(CC) stretching region (1655cm -1 ) was decreased during RFT. Furthermore, lower Raman intensity ratio of I 1655 /I 1442 , I 1655 /I 1745 that determine total unsaturation was also observed. Significant correlations (pRaman spectroscopy. Our result has proved that ESR and Raman spectroscopy showed great potential in characterizing lipid oxidation process of beef during RFT. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Dynamic characterization of small fibers based on the flexural vibrations of a piezoelectric cantilever probe

    International Nuclear Information System (INIS)

    Zhang, Xiaofei; Ye, Xuan; Li, Xide

    2016-01-01

    In this paper, we present a cantilever-probe system excited by a piezoelectric actuator, and use it to measure the dynamic mechanical properties of a micro- and nanoscale fiber. Coupling the fiber to the free end of the cantilever probe, we found the dynamic stiffness and damping coefficient of the fiber from the resonance frequency and the quality factor of the fiber-cantilever-probe system. The properties of Bacillus subtilis fibers measured using our proposed system agreed with tensile measurements, validating our method. Our measurements show that the piezoelectric actuator coupled to cantilever probe can be made equivalent to a clamped cantilever with an effective length, and calculated results show that the errors of measured natural frequency of the system can be ignored if the coupled fiber has an inclination angle of alignment of less than 10°. A sensitivity analysis indicates that the first or second resonant mode is the sensitive mode to test the sample’s dynamic stiffness, while the damping property has different sensitivities for the first four modes. Our theoretical analysis demonstrates that the double-cantilever probe is also an effective sensitive structure that can be used to perform dynamic loading and characterize dynamic response. Our method has the advantage of using amplitude-frequency curves to obtain the dynamic mechanical properties without directly measuring displacements and forces as in tensile tests, and it also avoids the effects of the complex surface structure and deformation presenting in contact resonance method. Our method is effective for measuring the dynamic mechanical properties of fiber-like one-dimensional (1D) materials. (paper)

  2. Dynamic characterization of small fibers based on the flexural vibrations of a piezoelectric cantilever probe

    Science.gov (United States)

    Zhang, Xiaofei; Ye, Xuan; Li, Xide

    2016-08-01

    In this paper, we present a cantilever-probe system excited by a piezoelectric actuator, and use it to measure the dynamic mechanical properties of a micro- and nanoscale fiber. Coupling the fiber to the free end of the cantilever probe, we found the dynamic stiffness and damping coefficient of the fiber from the resonance frequency and the quality factor of the fiber-cantilever-probe system. The properties of Bacillus subtilis fibers measured using our proposed system agreed with tensile measurements, validating our method. Our measurements show that the piezoelectric actuator coupled to cantilever probe can be made equivalent to a clamped cantilever with an effective length, and calculated results show that the errors of measured natural frequency of the system can be ignored if the coupled fiber has an inclination angle of alignment of less than 10°. A sensitivity analysis indicates that the first or second resonant mode is the sensitive mode to test the sample’s dynamic stiffness, while the damping property has different sensitivities for the first four modes. Our theoretical analysis demonstrates that the double-cantilever probe is also an effective sensitive structure that can be used to perform dynamic loading and characterize dynamic response. Our method has the advantage of using amplitude-frequency curves to obtain the dynamic mechanical properties without directly measuring displacements and forces as in tensile tests, and it also avoids the effects of the complex surface structure and deformation presenting in contact resonance method. Our method is effective for measuring the dynamic mechanical properties of fiber-like one-dimensional (1D) materials.

  3. Characterization of the electronic structure of C50Cl10 by means of soft x-ray spectroscopies

    International Nuclear Information System (INIS)

    Brena, Barbara; Luo Yi

    2005-01-01

    The electronic structure of the last synthesized fullerene molecule, the C 50 Cl 10 , has been characterized by theoretical simulation of x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and near-edge x-ray-absorption fine structure. All the calculations were performed at the gradient-corrected and hybrid density-functional theory levels. The combination of these techniques provides detailed information about the valence band and the unoccupied molecular orbitals, as well as about the carbon core orbitals

  4. Structural Characterization of Laboratory Made Tholins by IRMPD Action Spectroscopy and Ultrahigh Resolution Mass Spectrometry

    Science.gov (United States)

    Thissen, R.; Somogyi, A.; Vuitton, V.; Bégué, D.; Lemaire, J.; Steinmetz, V.

    2011-10-01

    The complex organic material that is found on the surface and within the haze layer of Titan is attributed to chemistry occurring in its thick N2/CH4 atmosphere. Although several groups are producing in various laboratory setting the socalled tholins which have been investigated by using analytical methods including UV/Vis, fluorescence, IR, and MS1-5, these very complex organic mixtures still hold many unanswered questions, especially related to the potentiality for their prebiotic chemistry. In addition to tholins characterization and analysis, we recently investigated quantitatively the hydrolysis kinetics of tholins in pure and NH3 containing water at different temperatures.7-8 Our groups at UJF (Grenoble) and at U of Arizona (Tucson) have been collaborating on mass spectral analyses of tholins samples for several years.9 Here, we report our most recent results on the structural characterization of tholins by infrared multiphoton dissociation (IRMPD) action spectroscopy10 and ultrahigh resolution MS. IRMPD action spectroscopy is a recently developed technique that uses IR photons of variable wavelengths to activate ions trapped inside an ion trap. When photons are absorbed at a given wavelength, the selected ion fragments and this fragmentation is monitored as a function of wavelength, analog to an absorption spectrum (impossible to record otherwise because of the much reduced density). This technique can, therefore, be used to determine IR spectra of ions in the gas phase, and provides with very acute structural information. IRMPD action spectroscopy is often used to distinguish between structural isomers of isobaric ions. The drawback is that it requests for high power lasers. Only two Free Electron Lasers (FEL) are available in the world and allow to record spectra with reasonable resolution (20-25 cm-1). IRMPD action spectra of selected ions from tholins will be presented and discussed together with observed fragmentation processes that reveal structural

  5. CuO and Co3O4 Nanoparticles: Synthesis, Characterizations, and Raman Spectroscopy

    Directory of Open Access Journals (Sweden)

    M. Rashad

    2013-01-01

    Full Text Available Copper oxide and cobalt oxide (CuO, Co3O4 nanocrystals (NCs have been successfully prepared in a short time using microwave irradiation without any postannealing treatment. Both kinds of nanocrystals (NCs have been prepared using copper nitrate and cobalt nitrate as the starting materials and distilled water as the solvent. The resulted powders of nanocrystals (NCs were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, scanning electron microscopy (SEM, and atomic force microscopy (AFM measurements. The obtained results confirm the presence of the both of oxides nanopowders produced during chemical precipitation using microwave irradiation. A strong emission under UV excitation is obtained from the prepared CuO and Co3O4 nanoparticles. The results show that the nanoparticles have high dispersion and narrow size distribution. The line scans of atomic force microscopy (AFM images of the nanocrystals (NCs sprayed on GaAs substrates confirm the results of both X-ray diffraction and transmission electron microscopy. Furthermore, vibrational studies have been carried out using Raman spectroscopic technique. Specific Raman peaks have been observed in the CuO and Co3O4 nanostructures, and the full width at half maximum (FWHM of the peaks indicates a small particle size of the nanocrystals.

  6. Optical characterization of pure vegetable oils and their biodiesels using Raman spectroscopy

    Science.gov (United States)

    Firdous, S.; Anwar, S.; Waheed, A.; Maraj, M.

    2016-04-01

    Great concern regarding energy resources and environmental polution has increased interest in the study of alternative sources of energy. Biodiesels as an alternative fuel provide a suitable diesel oil substitute for internal combustion engines. The Raman spectra of pure biodiesels of soybean oil, olive oil, coconut oil, animal fats, and petroleum diesel are optically characterized for quality and biofuel as an alternative fuel. The most significant spectral differences are observed in the frequency range around 1457 cm-1 for pure petroleum diesel, 1427 for fats biodiesel, 1670 cm-1 for pure soybean oil, 1461 cm-1 for soybean oil based biodiesel, 1670 cm-1 for pure olive oil, 1666 cm-1 for olive oil based biodiesel, 1461 cm-1 for pure coconut oil, and 1460 cm-1 for coconut oil based biodiesel, which is used for the analysis of the phase composition of oils. A diode pump solid-state laser with a 532 nm wavelength is used as an illuminating light. It is demonstrated that the peak positions and relative intensities of the vibrations of the oils can be used to identify the biodiesel quality for being used as biofuel.

  7. Optical characterization of pure vegetable oils and their biodiesels using Raman spectroscopy

    International Nuclear Information System (INIS)

    Firdous, S; Anwar, S; Waheed, A; Maraj, M

    2016-01-01

    Great concern regarding energy resources and environmental polution has increased interest in the study of alternative sources of energy. Biodiesels as an alternative fuel provide a suitable diesel oil substitute for internal combustion engines. The Raman spectra of pure biodiesels of soybean oil, olive oil, coconut oil, animal fats, and petroleum diesel are optically characterized for quality and biofuel as an alternative fuel. The most significant spectral differences are observed in the frequency range around 1457 cm −1 for pure petroleum diesel, 1427 for fats biodiesel, 1670 cm −1 for pure soybean oil, 1461 cm −1 for soybean oil based biodiesel, 1670 cm −1 for pure olive oil, 1666 cm −1 for olive oil based biodiesel, 1461 cm −1 for pure coconut oil, and 1460 cm −1 for coconut oil based biodiesel, which is used for the analysis of the phase composition of oils. A diode pump solid-state laser with a 532 nm wavelength is used as an illuminating light. It is demonstrated that the peak positions and relative intensities of the vibrations of the oils can be used to identify the biodiesel quality for being used as biofuel. (paper)

  8. Characterization of human breast disease using phosphorus magnetic resonance spectroscopy and proton magnetic resonance imaging

    International Nuclear Information System (INIS)

    Merchant, T.E.

    1992-01-01

    This thesis provides the fundamental characterization and differentiation of breast tissues using in vivo and ex vivo MR techniques in the hope that these techniques and experimental findings will be used on a larger scale and in a predictive manner in order to improve the specificity of diagnosis and treatment of breast cancer. In this dissertation, clinical studies were performed using proton magnetic resonance imaging and phosphorus magnetic resonance spectro-scopy ( 31 P MRS) to characterize and differentiate malignant breast tumors, benign breast tumors and normal breast tissues in vivo. These studies were carried out following the methodical characterization of chemical extracts of malignant breast tumor, benign breast tumor and normal breast parenchymal surgical tissue specimens using high resolution 31 P MRS. Alterations in breast tissue metabolism, as a result of pathological processes, were postulated to be responsible for measurable differences between malignant breast tumors, benign breast tumors and normal breast tissues using magnetic resonance techniques. (author). 365 refs.; 37 figs.; 25 tabs

  9. Characterizing free volumes and layer structures in polymeric membranes using slow positron annihilation spectroscopy

    International Nuclear Information System (INIS)

    Jean, Y C; Chen Hongmin; Awad, Somia; Zhang Sui; Chen Hangzheng; Lau, Cher Hon; Wang Huan; Li Fuyun; Chung, Tai-Shung; Lee, L James; Huang, James

    2011-01-01

    Positron annihilation spectroscopy coupled with a newly built slow positron beam at National University of Singapore has been used to study the free volume, pore, and depth profile (0 - 10 μm) in cellulose acetate polymeric membrane at the bottom and top sides of membranes for ionic separation in water purification applications. The S and R parameters from Doppler broadening energy of annihilation radiation representing free volumes (0.1-1 nm size) and pores (>1 nm-μm) as a function of depth have been analyzed into multilayers, i.e. skin dense, transition, and porous layers, respectively. The top side of membrane has large free volumes and pores and the bottom side has a skin dense layer, which plays a key role in membrane performance. Positron annihilation lifetime results provide additional information about free-volume size and distribution at the atomic and molecular scale in polymeric membrane systems. Doppler broadening energy and lifetime spectroscopies coupled with a variable mono-energy slow positron beam are sensitive and novel techniques for characterization of polymeric membrane in separation applications.

  10. Characterization of the Roraima savanna across of X-ray diffraction, thermomagnetic analysis and Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Gilmar A.; Araujo, R.C.; Sergio, C.S. [Universidade Federal de Roraima (UFRR), Boa Vista, RR (Brazil)

    2012-07-01

    Full text: The technique of X-ray diffraction has great resolving power to determine the phases present in crystalline material, thereby enabling it to determine the elements present in the materials as well as changes in structure that they can suffer when subjected to various physical processes and/or chemical means. The research had as objective to characterize the mineralogy of iron oxides, silicon, aluminum and other minerals in the soil of five points of the Roraima savannah. The points where samples were collected are five municipalities in the state of Roraima. The area of sampling is part of the savanna in Roraima. The samples were collected. We analyzed samples from five points from the collection of natural soil in the locations listed. The samples were placed in a mill to a uniform grain size. After the milling process, the magnetic material was separated using a permanent magnet. Then the samples were analyzed by x-ray diffraction, thermomagnetic analysis and Moessbauer spectroscopy. Preliminary results of XRD showed the occurrence of phases of oxides of iron, silicon, aluminum and other phases less. Thermomagnetic analysis show that the magnetic phases are magnetite and hematite. The results of the Moessbauer spectroscopy indicates the reliability in the two prior art and confirmed the presence of the phases of oxides of iron present in the soil analyzed. (author)

  11. Moessbauer Spectroscopy in the Characterization of waste product used like fertilizer in soil. Some Applications

    International Nuclear Information System (INIS)

    Furet, N. R.; Orihuela, D. L.; Hernandez

    2007-01-01

    At the present time, the use of industrial solid wastes is an important task, because a great effort that have been carried out to preserve the environmental and to obtain the high technologies. In this work, a characterization of a industrial waste product, on base of the monohydrous iron sulphate (FeSO 4 .1H 2 O) with a 15% approximately of free sulphuric acid, used like improvement of soil was carried out by Mossabuer spectroscopy. This waste product was used in a series of the experiences in parcels (where peaches, (Prunus persica), strawberries are cultivated) in the zone of Cartaya (Huelva, Spain). The characterisation of soil from the parcel before application of this product was carried out in order to analyse and compare with the final results by using the methods of the Moessbauer spectroscopy. High contents of Fe, S, and Zn at the studied product are observed . This elements are very important for plants. The pH in soil and Fe, Mn, and Zn contents in soil and leaf were determined. The knowledge of the main chemical-structural properties of this product, used like improvement of soil, will permit the study of the influence to) on the soil properly, b) on the peach leaves and c) on the foodstuff fruit. (Author)

  12. Optical properties and extinction spectroscopy to characterize the synthesis of amine capped silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Roldan, Maria Virginia [Laboratorio de Materiales Ceramicos, FCEIyA, IFIR, UNR, Rosario (Argentina)], E-mail: vroldan@fceia.unr.edu.ar; Scaffardi, Lucia B. [CIOp - CONICET, CIC, c.c. 124, 1900 La Plata (Argentina) and Area Departamental de Ciencias Basicas, Facultad de Ingenieria, Universidad Nacional de La Plata, La Plata (Argentina); Sanctis, Oscar de [Laboratorio de Materiales Ceramicos, FCEIyA, IFIR, UNR, Rosario (Argentina); Pellegri, Nora [Laboratorio de Materiales Ceramicos, FCEIyA, IFIR, UNR, Rosario (Argentina)], E-mail: pellegri@fceia.unr.edu.ar

    2008-12-20

    The present work describes a method for preparation of Ag nanoparticles from chemical reduction of AgNO{sub 3} in ethanol with ATS [N-[3-(trimethoxysilyl)propyl] diethylenetriamine] as surface modifier. We study the influence of different parameters such as concentration, time, temperature and reductor agents on the size and shape of the nanoparticles. We present the morphologic and structural characterization of samples by UV-vis extinction spectroscopy, Atomic Force Microscopy (AFM) and X-ray diffraction (XRD). Particularly, using optical extinction spectroscopy, the present work shows the analysis of size evolution in the fabrication process of spherical silver nanoparticles. This evolution is studied as a function of the time elapsed between the beginning of the reaction and the extraction of the sample (temporal delayed synthesis), and as a function of the temperature during the chemical reaction. In both the cases, we propose the study of the plasmon width as a useful, simple and inexpensive method for analysis of the mean radius, specially, for values below 6 nm.

  13. Optical properties and extinction spectroscopy to characterize the synthesis of amine capped silver nanoparticles

    International Nuclear Information System (INIS)

    Roldan, Maria Virginia; Scaffardi, Lucia B.; Sanctis, Oscar de; Pellegri, Nora

    2008-01-01

    The present work describes a method for preparation of Ag nanoparticles from chemical reduction of AgNO 3 in ethanol with ATS [N-[3-(trimethoxysilyl)propyl] diethylenetriamine] as surface modifier. We study the influence of different parameters such as concentration, time, temperature and reductor agents on the size and shape of the nanoparticles. We present the morphologic and structural characterization of samples by UV-vis extinction spectroscopy, Atomic Force Microscopy (AFM) and X-ray diffraction (XRD). Particularly, using optical extinction spectroscopy, the present work shows the analysis of size evolution in the fabrication process of spherical silver nanoparticles. This evolution is studied as a function of the time elapsed between the beginning of the reaction and the extraction of the sample (temporal delayed synthesis), and as a function of the temperature during the chemical reaction. In both the cases, we propose the study of the plasmon width as a useful, simple and inexpensive method for analysis of the mean radius, specially, for values below 6 nm

  14. Detection Limits of DLS and UV-Vis Spectroscopy in Characterization of Polydisperse Nanoparticles Colloids

    Directory of Open Access Journals (Sweden)

    Emilia Tomaszewska

    2013-01-01

    Full Text Available Dynamic light scattering is a method that depends on the interaction of light with particles. This method can be used for measurements of narrow particle size distributions especially in the range of 2–500 nm. Sample polydispersity can distort the results, and we could not see the real populations of particles because big particles presented in the sample can screen smaller ones. Although the theory and mathematical basics of DLS technique are already well known, little has been done to determine its limits experimentally. The size and size distribution of artificially prepared polydisperse silver nanoparticles (NPs colloids were studied using dynamic light scattering (DLS and ultraviolet-visible (UV-Vis spectroscopy. Polydisperse colloids were prepared based on the mixture of chemically synthesized monodisperse colloids well characterized by atomic force microscopy (AFM, transmission electron microscopy (TEM, DLS, and UV-Vis spectroscopy. Analysis of the DLS results obtained for polydisperse colloids reveals that several percent of the volume content of bigger NPs could screen completely the presence of smaller ones. The presented results could be extremely important from nanoparticles metrology point of view and should help to understand experimental data especially for the one who works with DLS and/or UV-Vis only.

  15. Characterization of the Pore Filling of Solid State Dye Sensitized Solar Cells with Photoinduced Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Carol Olson

    2011-01-01

    Full Text Available Near steady-state photoinduced absorption (PIA and UV-Vis absorption spectroscopy are used to characterize the pore filling of spiro-MeOTAD (2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine9,9′-spirobifluorene into the nanoparticulate TiO2 electrode of a solid-state dye-sensitized solar cell (ssDSC. The volumetric ratio of filled to unfilled pore volumes, as well as the optical signature of interacting chemical species, that is, the hole-transfer yield (HTY, are investigated. PIA spectroscopy is used to measure the HTY, relative to the amount of spiro-MeOTAD present, without needing to determine the extinction coefficients of the dye and spiro-MeOTAD cation species. The Beer-Lambert law is used to relate the relative PIA signal to the penetration length of the hole-conductor in the TiO2 film. For the sample thickness range of 1.4–5 μm investigated here, the optimum characteristic penetration length is determined to be 3.1+0.46 μm, which is compared to 1.4 μm for the 200 mg mL−1 concentration of spiro-MeOTAD conventionally used. Therefore, doubling the effective penetration of spiro-MeOTAD is necessary to functionalize all the dye molecules in a ssDSC.

  16. High-resolution Raman Spectroscopy for the Nanostructural Characterization of Explosive Nanodiamond Precursors.

    Science.gov (United States)

    Deckert-Gaudig, Tanja; Pichot, Vincent; Spitzer, Denis; Deckert, Volker

    2017-01-18

    The specific attributes of nanodiamonds have attracted increasing interest for electronics or biomedical applications. An efficient synthetic route towards nanodiamonds is via detonation of hexolite (i.e. a mixture of TNT [2,4,6-trinitrotoluene] and RDX [1,3,5-trinitro-1,3,5-triazine]). In particular, detonation of hexolite crystallized by spray flash evaporation (SFE) yields extremely small diamonds (<4 nm). To unravel the detonation mechanism, a structural characterization of the explosives is required but is challenging due to their thermal instability. We demonstrate a combination of conventional Raman spectroscopy and tip-enhanced Raman spectroscopy (TERS) for resolving morphological and structural differences of differently prepared hexolite nanocomposites. The experiments allow for the first time a structural differentiation of individual TNT and RDX crystals and 15-20 nm sized core-shell structures, consequently providing a general approach to investigate the actual composition of mixtures on the nanometer scale. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Advanced techniques for actinide spectroscopy (ATAS 2012). Abstract book

    Energy Technology Data Exchange (ETDEWEB)

    Foerstendorf, Harald; Mueller, Katharina; Steudtner, Robin [eds.

    2012-07-01

    The abstract book of the International workshop on advanced techniques for actinide spectroscopy (ATAS 2012) include contributions concerning the following issues: environmental applications, NMR spectroscopy, vibrational spectroscopy, X-ray spectroscopy and theory, technical application: separation processes, emission spectroscopy.

  18. Advanced techniques for actinide spectroscopy (ATAS 2012). Abstract book

    International Nuclear Information System (INIS)

    Foerstendorf, Harald; Mueller, Katharina; Steudtner, Robin

    2012-01-01

    The abstract book of the International workshop on advanced techniques for actinide spectroscopy (ATAS 2012) include contributions concerning the following issues: environmental applications, NMR spectroscopy, vibrational spectroscopy, X-ray spectroscopy and theory, technical application: separation processes, emission spectroscopy.

  19. X-ray diffraction, IR spectroscopy and thermal characterization of partially hydrolyzed guar gum.

    Science.gov (United States)

    Mudgil, Deepak; Barak, Sheweta; Khatkar, B S

    2012-05-01

    Guar gum was hydrolyzed using cellulase from Aspergillus niger at 5.6 pH and 50°C temperature. Hydrolyzed guar gum sample was characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, dilute solution viscometry and rotational viscometry. Viscometry analysis of native guar gum showed a molecular weight of 889742.06, whereas, after enzymatic hydrolysis, the resultant product had a molecular weight of 7936.5. IR spectral analysis suggests that after enzymatic hydrolysis of guar gum there was no major transformation of functional group. Thermal analysis revealed no major change in thermal behavior of hydrolyzed guar gum. It was shown that partial hydrolysis of guar gum could be achieved by inexpensive and food grade cellulase (Aspergillus niger) having commercial importance and utilization as a functional soluble dietary fiber for food industry. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Tissue characterization using electrical impedance spectroscopy data: a linear algebra approach.

    Science.gov (United States)

    Laufer, Shlomi; Solomon, Stephen B; Rubinsky, Boris

    2012-06-01

    In this study, we use a new linear algebra manipulation on electrical impedance spectroscopy measurements to provide real-time information regarding the nature of the tissue surrounding the needle in minimal invasive procedures. Using a Comsol Multiphysics three-dimensional model, a phantom based on ex vivo animal tissue and in vivo animal data, we demonstrate how tissue inhomogeneity can be characterized without any previous knowledge of the electrical properties of the different tissues, except that they should not be linearly dependent on a certain frequency range. This method may have applications in needle biopsies, radiation seeds, or minimally invasive surgery and can reduce the number of computer tomography or magnetic resonance imaging images. We conclude by demonstrating how this mathematical approach can be useful in other applications.