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Sample records for generation vibrational spectroscopy

  1. 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

  2. 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...

  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. 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

  5. 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)

  6. 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.

  7. 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

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.)

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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)

  8. 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.

  9. 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.

  10. 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

  11. 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.

  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. 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.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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...

  16. 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

  17. 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)

  18. 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.

  19. 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

  20. The structure of oleamide films at the aluminum/oil interface and aluminum/air interface studied by Sum Frequency Generation (SFG) vibrational spectroscopy and Reflection Absorption Infrared Spectroscopy (RAIRS).

    Science.gov (United States)

    Casford, Michael T L; Davies, Paul B

    2009-08-01

    The structure of oleamide (cis-9-octadecenamide) films on aluminum has been investigated by sum frequency generation vibrational spectroscopy (SFG) and reflection absorption infrared spectroscopy (RAIRS). Three different film deposition strategies were investigated: (i) films formed by equilibrium adsorption from oleamide solutions in oil, (ii) Langmuir-Blodgett films cast at 1 and 25 mN m(-1), (iii) thick spin-cast films. Both L-B and spin-cast films were examined in air and under oil. The adsorbate formed in the 1 mN m(-1) film in air showed little orientational order. For this film, the spectroscopic results and the ellipsometric thickness point to a relatively conformationally disordered monolayer that is oriented principally in the plane of the interface. Direct adsorption to the metal interface from oil results in SFG spectra of oleamide that are comparable to those observed for the 1 mN m(-1) L-B film in air. In contrast, SFG and RAIRS results for the 25 mN m(-1) film in air and SFG spectra of the spin-cast film in air both show strong conformational ordering and orientational alignment normal to the interface. The 25 mN m(-1) film has an ellipsometric thickness almost twice that of the 1 mN m(-1) L-B film. Taken in combination with the spectroscopic results, this is indicative of a well packed monolayer in air in which the hydrocarbon chain is in an essentially defect-free extended conformation with the methyl terminus oriented away from the surface. A similar structure is also deduced for the surface of the spin-cast film in air. Upon immersion of the 25 mN m(-1) L-B film in oil the SFG spectra show that this film rapidly adopts a relatively disordered structure similar to that seen for the 1 mN m(-1) L-B film in air. Immersion of the spin-cast film in oil results in the gradual disordering of the amide film over a period of several days until the observed spectra become essentially identical to those observed for direct adsorption of oleamide from oil.

  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. 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

  3. 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.

  4. 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.

    2015-01-14

    © 2014 American Chemical Society. 1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO2 shells at 20, 60, and 100 °C. The core-shells were grown around polyvinylpyrrolidone (PVP) coated 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 in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO2 (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and cis/trans-2-butene) to Pd@SiO2 (1,3-BD favors one path and produces 1-butene and cis/trans-2-butene). In contrast to Pt@SiO2 and Pd@SiO2, SFG and kinetic experiments of Rh@SiO2 show a permanent accumulation of organic material.

  5. 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

  6. 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.

  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. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Limerick Nuclear Generating Station vibration monitoring system

    International Nuclear Information System (INIS)

    Mikulski, R.

    1988-01-01

    Philadelphia Electric Company utilizes a vibration monitoring computer system at its Limerick Nuclear Generating Station to evaluate machine performance. Performance can be evaluated through instantaneous sampling, online static and transient data. The system functions as an alarm monitor, displaying timely alarm data to the control area. The passage of time since the system's inception has been a learning period. Evaluation through continuous use has led to many enhancements in alarm handling and in the acquisition and display of machine data. Due to the system's sophistication, a routine maintenance program is a necessity. This paper describes the system's diagnostic tools and current utilization. System development and maintenance techniques will also be discussed

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. Dependence of steam generator vibrations on feedwater pressure

    International Nuclear Information System (INIS)

    Sadilek, J.

    1989-01-01

    Vibration sensors are attached to the bottom of the steam generator jacket between the input and output primary circuit collectors. The effective vibration value is recorded daily. Several times higher vibrations were observed at irregular intervals; their causes were sought, and the relation between the steam generator vibrations measured at the bottom of its vessel and the feedwater pressure was established. The source of the vibrations was found to be in the feedwater tract of the steam generator. The feedwater tract is described and its hydraulic characteristics are given. Vibrations were measured on the S02 valve. It is concluded that vibrations can be eliminated by reducing the water pressure before the control valves and by replacing the control valves with ones with more suitable control characteristics. (E.J.). 3 figs., 1 tab., 3 refs

  20. 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

  1. Vibration analysis of a hydro generator for different operating regimes

    Science.gov (United States)

    Haţiegan, C.; Pădureanu, I.; Jurcu, M.; Nedeloni, M. D.; Hamat, C. O.; Chioncel, C. P.; Trocaru, S.; Vasile, O.; Bădescu, O.; Micliuc, D.; (Filip Nedeloni, L.; Băra, A.; (Barboni Haţiegan, L.

    2017-01-01

    Based on experimental measurements, this paper presents the vibration analysis of a hydro generator that equips a Kaplan hydraulic turbine of a Hydropower plant in Romania. This analysis means vibrations measurement to different operating regimes of the hydro generator respectively before installing it and into operation, namely putting off load mode (unexcited and excited) respectively putting on load mode. By comparing, through the experimental results obtained before and after the operation of hydro aggregates are observed vibrations improvements.

  2. Anti-vibration bars for nuclear steam generators

    International Nuclear Information System (INIS)

    Gowda, B.V.; Wilson, R.M.; Wepfer, R.M.

    1986-01-01

    A method of installing tubular anti-vibration bars into a tube bundle of a steam generator wherein the tube bundle comprises rows of tubes, with the anti-vibration bars received between adjacent rows of the tube bundle for stabilizing the tubes against vibration. The anti-vibration bars are first inserted between adjacent rows of the tube bundle and a pressurized fluid is then introduced into the anti-vibration bars which are thus expanded into contact with the tubes of the adjacent rows for support

  3. 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.

  4. Vibration monitoring of large generator stator and-winding

    International Nuclear Information System (INIS)

    Duffeau, F.; Bernard, P.

    1999-01-01

    Large generators of French Nuclear Power plants are equipped with a standardised vibration monitoring system. The first aim of these new systems is to protect the machines by generating alarms in the control room when predefined vibration thresholds have been over-passed. Secondly, this specially designed instrumentation permits to create a National data base allowing to compare different generators of the same technology. Additionally, statistical methods have been developed in order to 'guess' vibration level at several locations of the stator end-windings, depending on the actual operating parameters of the generator, i.e. reactive and active power load. So this paper presents the general concept of the vibration monitoring of EDF large generator stators and deals with a new method to predict vibrations in different locations under control. (authors)

  5. 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

  6. In-situ Studies of the Reactions of Bifunctional and Heterocyclic Molecules over Noble Metal Single Crystal and Nanoparticle Catalysts Studied with Kinetics and Sum-Frequency Generation Vibrational Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-06-30

    Sum frequency generation surface vibrational spectroscopy (SFG-VS) in combination with gas chromatography (GC) was used in-situ to monitor surface bound reaction intermediates and reaction selectivities for the hydrogenation reactions of pyrrole, furan, pyridine, acrolein, crotonaldehyde, and prenal over Pt(111), Pt(100), Rh(111), and platinum nanoparticles under Torr reactant pressures and temperatures of 300K to 450K. The focus of this work is the correlation between the SFG-VS observed surface bound reaction intermediates and adsorption modes with the reaction selectivity, and how this is affected by catalyst structure and temperature. Pyrrole hydrogenation was investigated over Pt(111) and Rh(111) single crystals at Torr pressures. It was found that pyrrole adsorbs to Pt(111) perpendicularly by cleaving the N-H bond and binding through the nitrogen. However, over Rh(111) pyrrole adsorbs in a tilted geometry binding through the {pi}-aromatic orbitals. A surface-bound pyrroline reaction intermediate was detected over both surfaces with SFG-VS. It was found that the ring-cracking product butylamine is a reaction poison over both surfaces studied. Furan hydrogenation was studied over Pt(111), Pt(100), 10 nm cubic platinum nanoparticles and 1 nm platinum nanoparticles. The product distribution was observed to be highly structure sensitive and the acquired SFG-VS spectra reflected this sensitivity. Pt(100) exhibited more ring-cracking to form butanol than Pt(111), while the nanoparticles yielded higher selectivities for the partially saturated ring dihydrofuran. Pyridine hydrogenation was investigated over Pt(111) and Pt(100). The α-pyridyl surface adsorption mode was observed with SFG-VS over both surfaces. 1,4-dihydropyridine was seen as a surface intermediate over Pt(100) but not Pt(111). Upon heating the surfaces to 350K, the adsorbed pyridine changes to a flat-lying adsorption mode. No evidence was found for the pyridinium cation. The hydrogenation of the

  7. Simulation Study on Material Property of Cantilever Piezoelectric Vibration Generator

    Directory of Open Access Journals (Sweden)

    Yan Zhen

    2014-06-01

    Full Text Available For increasing generating capacity of cantilever piezoelectric vibration generator with limited volume, relation between output voltage, inherent frequency and material parameter of unimorph, bimorph in series type and bimorph in parallel type piezoelectric vibration generator is analyzed respectively by mechanical model and finite element modeling. The results indicate PZT-4, PZT- 5A and PZT-5H piezoelectric materials and stainless steel, nickel alloy substrate material should be firstly chosen.

  8. [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.

  9. Effect of mechanical vibration generated in oscillating/vibratory ...

    African Journals Online (AJOL)

    Background: Whole body vibration (WBV) exercise has been used in health sciences. Authors have reported that changes on the concentration of plasma biomarkers could be associated with the WBV effects. The aim of this investigation is to assess the consequences of exposition of 25 Hz mechanical vibration generated ...

  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. 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

  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. 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))).

  14. 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.

  15. 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.

  16. Theoretical and experimental study of vibration, generated by monorail trains

    Science.gov (United States)

    Rybak, Samuil A.; Makhortykh, Sergey A.; Kostarev, Stanislav A.

    2002-11-01

    Monorail transport as all other city transport vehicles is the source of high noise and vibration levels. It is less widespread than cars or underground transport but its influence in modern cities enhances. Now in Moscow the first monorail road with trains on tires is designed, therefore the problem of vibration and noise assessments and prediction of its impact on the residential region appears. To assess the levels of generated vibration a physical model of interaction in the system wagon-tire-road coating-viaduct-soil has been proposed and then numerically analyzed. The model is based on the known from publications facts of automobile transport vibration and our own practice concerning underground trains vibration generation. To verify computer simulation results and adjust model parameters the series of measurements of noise and vibration near experimental monorail road was carried out. In the report the results of calculations and measurements will be presented and some outcomes of possible acoustical ecologic situation near monorail roads will be proposed.

  17. Vibrations measurement at the Embalse nuclear power plant's electrical generator

    International Nuclear Information System (INIS)

    Salomoni, R.C.; Belinco, C.G.; Pastorini, A.J.; Sacchi, M.A.

    1987-01-01

    After the modifications made at the Embalse nuclear power plant's electrical generator to reduce its vibration level produced by electromagnetic phenomena, it was necessary to perform measurements at the new levels, under different areas and power conditions. To this purpose, a work was performed jointly with the 'Vibrations Team' of the ANSALDO Company (the generator constructor) and the Hydrodynamic Assays Division under the coordination and supervision of the plant's electrical maintenance responsible. This paper includes the main results obtained and the instrumentation criteria and analysis performed. (Author)

  18. Analysis of tube vibrations in D-4 steam generator

    International Nuclear Information System (INIS)

    Mavko, B.; Peterlin, G.; Boltezar, M.

    1983-01-01

    Accelerometer data for the most exposed tube in steam generator D-4 were recorded on magnetic tape. Procedures for calculations of the most characteristic parameters were prepared for spectral analyzer on SD 360. Parameters which most satisfactorily describe the vibrations are power spectral densities peak to peak acceleration volume and root mean square displacement. Computer program was written to calculate the natural frequencies of a multispaned tube. Procedures and the computer program will be used for independent analysis of tube vibrations in Krsko D-4 type steam generator. (author)

  19. Capacitance-Based Frequency Adjustment of Micro Piezoelectric Vibration Generator

    Directory of Open Access Journals (Sweden)

    Xinhua Mao

    2014-01-01

    Full Text Available Micro piezoelectric vibration generator has a wide application in the field of microelectronics. Its natural frequency is unchanged after being manufactured. However, resonance cannot occur when the natural frequencies of a piezoelectric generator and the source of vibration frequency are not consistent. Output voltage of the piezoelectric generator will sharply decline. It cannot normally supply power for electronic devices. In order to make the natural frequency of the generator approach the frequency of vibration source, the capacitance FM technology is adopted in this paper. Different capacitance FM schemes are designed by different locations of the adjustment layer. The corresponding capacitance FM models have been established. Characteristic and effect of the capacitance FM have been simulated by the FM model. Experimental results show that the natural frequency of the generator could vary from 46.5 Hz to 42.4 Hz when the bypass capacitance value increases from 0 nF to 30 nF. The natural frequency of a piezoelectric vibration generator could be continuously adjusted by this method.

  20. Capacitance-based frequency adjustment of micro piezoelectric vibration generator.

    Science.gov (United States)

    Mao, Xinhua; He, Qing; Li, Hong; Chu, Dongliang

    2014-01-01

    Micro piezoelectric vibration generator has a wide application in the field of microelectronics. Its natural frequency is unchanged after being manufactured. However, resonance cannot occur when the natural frequencies of a piezoelectric generator and the source of vibration frequency are not consistent. Output voltage of the piezoelectric generator will sharply decline. It cannot normally supply power for electronic devices. In order to make the natural frequency of the generator approach the frequency of vibration source, the capacitance FM technology is adopted in this paper. Different capacitance FM schemes are designed by different locations of the adjustment layer. The corresponding capacitance FM models have been established. Characteristic and effect of the capacitance FM have been simulated by the FM model. Experimental results show that the natural frequency of the generator could vary from 46.5 Hz to 42.4 Hz when the bypass capacitance value increases from 0 nF to 30 nF. The natural frequency of a piezoelectric vibration generator could be continuously adjusted by this method.

  1. 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.

  2. 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.

  3. Two-phase flow induced vibrations in CANDU steam generators

    International Nuclear Information System (INIS)

    Gidi, A.

    2009-01-01

    The U-Bend region of nuclear steam generators tube bundles have suffered from two-phase cross flow induced vibrations. Tubes in this region have experienced high amplitude vibrations leading to catastrophic failures. Turbulent buffeting and fluid-elastic instability has been identified as the main causes. Previous investigations have focused on flow regime and two-phase flow damping ratio. However, tube bundles in steam generators have vapour generated on the surface of the tubes, which might affect the flow regime, void fraction distribution, turbulent intensity levels and tube-flow interaction, all of which have the potential to change the tube vibration response. A cantilevered tube bundle made of electric cartridges heaters was built and tested in a Freon-11 flow loop at McMaster University. Tubes were arranged in a parallel triangular configuration. The bundle was exposed to two-phase cross flows consisting of different combinations of void from two sources, void generated upstream of the bundle and void generated at the surface of the tubes. Tube tip vibration response was measured optically and void fraction was measured by gamma densitometry technique. It was found that tube vibration amplitude in the transverse direction was reduced by a factor of eight for void fraction generated at the tube surfaces only, when compared to the upstream only void generation case. The main explanation for this effect is a reduction in the correlation length of the turbulent buffeting forcing function. Theoretical calculations of the tube vibration response due to turbulent buffeting under the same experimental conditions predicted a similar reduction in tube amplitude. The void fraction for the fluid-elastic instability threshold in the presence of tube bundle void fraction generation was higher than that for the upstream void fraction generation case. The first explanation of this difference is the level of turbulent buffeting forces the tube bundle was exposed to

  4. Generation of three-mode nonclassical vibrational states of ions

    International Nuclear Information System (INIS)

    Nguyen Ba An; Truong Minh Duc

    2002-01-01

    We propose using eight lasers with appropriate orientations and conditions to generate stable trio coherent states of an ion in a three-dimensional isotropic trap. Seven lasers whose orientations are important should be detuned to the third lower sideband of the ion vibrational motion. The eighth laser whose direction is not important should be in resonance with the ionic transition

  5. 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.

  6. Laboratory evaluation of a vibrating orifice monodisperse aerosol generator

    International Nuclear Information System (INIS)

    Everitt, N.M.; Snelling, K.W.

    1985-02-01

    The Berglund-Liu vibrating orifice aerosol generator is capable of producing monodisperse particles in the diameter range 5 to 50 μm. Experiments have been carried out to set up and evaluate such a generator for the preparation of standard liquid (olive oil) and solid (methylene blue) aerosols in the size range 8 to 13 μm. Modifications have been made to the apparatus to improve its performance and increase its particle output. (author)

  7. Anti-vibration bars for nuclear steam generators

    International Nuclear Information System (INIS)

    Gowda, B.V.; Wilson, R.M.; Wepfer, R.M.

    1988-01-01

    This patent describes anti-vibrations bars structurally supporting tubes carrying high-temperature coolant in a steam generator, the antivibration bars being disposed between adjacent rows of tubes and expanded from a rest state to an expanded state as pressure is applied to the interior of the anti-vibration bars, each of the anti-vibration bars being configured as a hollow member of a rectangular shape. The rectangular shape comprising a pair of opposing wall lengths and a pair of opposing wall widths, each of the wall lengths have a thickness greater than that of the wall widths to facilitate expansion of the opposing wall lengths away from each other and into contact respectively with tubes of adjacent rows, the wall lengths having sufficient rigidity to resist deformation as the bars are expanded to their expanded state so that the wall lengths make a line contact with their respective tubes

  8. Vibration Analysis for Steam Dryer of APR1400 Steam Generator

    Energy Technology Data Exchange (ETDEWEB)

    Han, Sung-heum; Ko, Doyoung [KHNP CRI, Daejeon (Korea, Republic of); Cho, Minki [Doosan Heavy Industry, Changwon (Korea, Republic of)

    2016-10-15

    This paper is related to comprehensive vibration assessment program for APR1400 steam generator internals. According to U.S. Nuclear Regulatory Commission, Regulatory Guide 1.20 (Rev.3, March 2007), we conducted vibration analysis for a steam dryer as the second steam separator of steam generator internals. The vibration analysis was performed at the 100 % power operating condition as the normal operation condition. The random hydraulic loads were calculated by the computational fluid dynamics and the structural responses were predicted by power spectral density analysis for the probabilistic method. In order to meet the recently revised U.S. NRC RG 1.20 Rev.3, the CVAP against the potential adverse flow effects in APR1400 SG internals should be performed. This study conducted the vibration response analysis for the SG steam dryer as the second moisture separator at the 100% power condition, and evaluated the structural integrity. The predicted alternating stress intensities were evaluated to have more than 17.78 times fatigue margin compared to the endurance limit.

  9. Resolution of torsional vibration issue for large turbine generators

    International Nuclear Information System (INIS)

    Evans, D.G.; Giesecke, H.D.; Willman, E.C.; Moffitt, S.P.

    1995-01-01

    The excitation of turbine generator torsional natural frequencies in the region near 120 Hz by electrical transients in the power system has resulted in blade failures for several large 1,800 rpm nuclear turbines. At Cleveland Electric's Perry Nuclear Power plant a combination of advanced measurement techniques and analyses were used to identify and resolve a potential torsional vibration problem without adverse impact on the plant availability. The Perry turbine generator consists of a high pressure turbine, three low pressure turbines with 43 inch last stage blades, and a 1,250 MWe four pole generator operating at 1,800 rpm. Torsional vibration measurements obtained from random vibration during operation were acquired just prior to the 1994 refueling outage. The measurements indicated that the 26th torsional mode of vibration was just under 120 Hz and within the range of frequencies for which the manufacturer recommends modifying the unit to shift the problem torsional natural frequency. Extensive analytical modeling was used to design a modification to shift the torsional natural frequencies away from 120 Hertz and the modification was implemented during the refueling outage without affecting outage critical path. An off-line ramp test and additional on-line monitoring performed at the conclusion of the outage confirmed that the on-line method provided accurate measurements of the torsional natural frequencies and demonstrated that, with the modification, the torsional natural frequencies were sufficiently removed from 120 Hertz to allow turbine generator operation. The modification, which involved brazing of the tie wires on all last stage blades, also significantly reduces the stress on the last stage blades that result from negative sequence currents, further increasing the operating margin of the turbine generator with respect to electrical transients and faults

  10. 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.

  11. Vibration power generator for a linear MR damper

    International Nuclear Information System (INIS)

    Sapiński, Bogdan

    2010-01-01

    The paper describes the structure and the results of numerical calculations and experimental tests of a newly developed vibration power generator for a linear magnetorheological (MR) damper. The generator consists of permanent magnets and coil with foil winding. The device produces electrical energy according to Faraday's law of electromagnetic induction. This energy is applied to vary the damping characteristics of the MR damper attached to the generator by the input current produced by the device. The objective of the numerical calculations was to determine the magnetic field distribution in the generator as well as the electric potential and current density in the generator's coil during the idle run and under the load applied to the MR damper control coil. The results of the calculations were used during the design and manufacturing stages of the device. The objective of the experimental tests carried out on a dynamic testing machine was to evaluate the generator's efficiency and to compare the experimental and predicted data. The experimental results demonstrate that the engineered device enables a change in the kinetic energy of the reciprocal motion of the MR damper which leads to variations in the damping characteristics. That is why the generator may be used to build up MR damper based vibration control systems which require no external power

  12. 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

  13. 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)

  14. 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

  15. 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.)

  16. 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

  17. 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

  18. Flow-induced vibration in LMFBR steam generators: a state-of-the-art review

    International Nuclear Information System (INIS)

    Shin, Y.S.; Wambsganss, M.W.

    1975-05-01

    This state-of-the-art review identifies and discusses existing methods of flow-induced vibration analysis applicable to steam generators, their limitations, and base-technology needs. Also included are discussions of five different LMFBR steam-generator configurations and important design considerations, failure experiences, possible flow-induced excitation mechanisms, vibration testing, and available methods of vibration analysis. The objectives are to aid LMFBR steam-generator designers in making the best possible evaluation of potential vibration in steam-generator internals, and to provide the basis for development of design guidelines to avoid detrimental flow-induced vibration

  19. 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

  20. 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…

  1. 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

  2. Vibration and wear characteristics of steam generator tubes

    International Nuclear Information System (INIS)

    Choi, Young Hwan

    2003-06-01

    This study investigates the fluid elastic instability characteristics of Steam Generator (SG) U-tubes with defect and the safety assessment of the potential for fretting-wear damages on Steam Generator (SG) U-tubes caused by foreign object in operating nuclear power plants. The operating SG shell-side flow field conditions for determining the fluid elastic instability or fretting-wear parameters such as damping ratio, added mass and flow velocity are obtained from three-dimensional SG flow calculation using the ATHOS3 code. To get the natural frequency, corresponding mode shape and participation factor, modal analyses are performed for the U-tubes either with axial or circumferential flaw with different sizes. Special emphases are on the effects of flaw orientation and size on the modal and instability characteristics of tubes, which are expressed in terms of the natural frequency, corresponding mode shape and stability ratio. Also, the wear rate of U-tube caused by foreign object is calculated using the Archard formula and the remaining life of the tube is predicted, and discussed in this study is the effect of the flow velocity and vibration of the tube on the remaining life of the tube. In addition, addressed is the effect of the internal pressure on the vibration and fretting-wear characteristics of the tube

  3. Substantiation of vibration strength of nuclear reactor and steam generator internals. Main problems

    International Nuclear Information System (INIS)

    Fyodorov, V.G.; Sinyavasky, V.F.

    1977-01-01

    The report details the scope and priority of studies necessary for substantiation of vibration strength of steam generator tube bundles and reactor fuel assemblies, and design modifications helping to reduce flow-induced vibration of the internals specified. Steam generator tube bundles are studied on the basis of a standard establishing vibration requirements at various stages of design, manufacture and operation of a steam generator at a nuclear power station. The main vibration characteristics of tubes obtained through model and full-scale tests are compared with calculation results. Results are provided concerning test-stand vibration tests of fuel elements and fuel assemblies. (author)

  4. 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...

  5. 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

  6. 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

  7. 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...

  8. Mobile phone generated vibrations used to detect diabetic peripheral neuropathy.

    Science.gov (United States)

    May, Jonathan David; Morris, Matthew William John

    2017-12-01

    In the current United Kingdom population the incidence of diabetic peripheral neuropathy is increasing. The presence of diabetic neuropathy affects decision making and treatment options. This study seeks to evaluate if the vibrations generated from a mobile phone can be used to screen patients for diabetic peripheral neuropathy. This study comprised of 61 patients; a control group of 21 patients; a lower limb injury group of 19 patients; a diabetic peripheral neuropathy group of 21 patients. The control and injury group were recruited randomly from fracture clinics. The diabetic peripheral neuropathy group were randomly recruited from the diabetic foot clinic. The 61 patients were examined using a 10g Semmes-Weinstein monofilament, a 128Hz tuning fork and a vibrating mobile phone. The points tested were, index finger, patella, lateral malleoli, medial malleoli, heel, first and fifth metatarsal heads. The most accurate location of all the clinical tests was the head of the 1st metatarsal at 0.86. The overall accuracy of the tuning fork was 0.77, the ten gram monofilament 0.79 and the mobile phone accuracy was 0.88. The control group felt 420 of 441 tests (95%). The injury group felt 349 of 399 tests (87%). The neuropathic group felt 216 of 441 tests (48%). There is a significant difference in the number of tests felt between the control and both the injury and neuropathic groups. pperipheral neuropathy. The most accurate location to test for diabetic peripheral neuropathy is the head of the 1st metatarsal. Screening for diabetic peripheral neuropathy in the index finger and patella were inaccurate. An injury to the lower limb affects the patient's vibration sensation, we would therefore recommend screening the contralateral limb to the injury. This study represents level II evidence of a new diagnostic investigation. Copyright © 2016 European Foot and Ankle Society. All rights reserved.

  9. 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

  10. Diagnosis of excessive vibration signals of two-pole generator rotors in balancing

    International Nuclear Information System (INIS)

    Park, Jong Po

    2000-01-01

    Cause of excessive vibration with twice the rotational speed of a two-pole generator rotor for the fossil power plants was investigated. The two-pole generator rotor, treated as a typically asymmetric rotor in vibration analysis, produces asynchronous vibration with twice the rotational speed, sub-harmonic critical speeds, and potentially unstable operating zones due to its own inertia and/or stiffness asymmetry. This paper introduces a practical balancing procedure, and presents the results of the investigation on sources of the excessive vibration based on the experimental vibration data of the asymmetric two-pole rotor in balancing

  11. Fueled viking generator S/N 106 acceptance vibration test report

    International Nuclear Information System (INIS)

    Anderson, C.; Brewer, C.O.; Abrahamson, S.G.

    1976-01-01

    The Viking Generator S/N 106 was vibrated to the Teledyne Isotope Flight Acceptance Schedule (Random Only) with no deviation from normal generator functional output. Radiographic analysis and power tests before and after the vibration test indicated no change in the condition of the generator. The work was conducted in the Alpha Fuels Environmental Test Facility at Mound Laboratory

  12. Vibration Spectrum Analysis for Indicating Damage on Turbine and Steam Generator Amurang Unit 1

    Directory of Open Access Journals (Sweden)

    Beny Cahyono

    2017-12-01

    Full Text Available Maintenance on machines is a mandatory asset management activity to maintain asset reliability in order to reduce losses due to failure. 89% of defects have random failure mode, the proper maintenance method is predictive maintenance. Predictive maintenance object in this research is Steam Generator Amurang Unit 1, which is predictive maintenance is done through condition monitoring in the form of vibration analysis. The conducting vibration analysis on Amurang Unit 1 Steam Generator is because vibration analysis is very effective on rotating objects. Vibration analysis is predicting the damage based on the vibration spectrum, where the vibration spectrum is the result of separating time-based vibrations and simplifying them into vibrations based on their frequency domain. The transformation of time-domain-wave into frequency-domain-wave is using the application of FFT, namely AMS Machinery. The measurement of vibration value is done on turbine bearings and steam generator of Unit 1 Amurang using Turbine Supervisory Instrument and CSI 2600 instrument. The result of this research indicates that vibration spectrum from Unit 1 Amurang Power Plant indicating that there is rotating looseness, even though the vibration value does not require the Unit 1 Amurang Power Plant to stop operating (shut down. This rotating looseness, at some point, can produce some indications that similar with the unbalance. In order to avoid more severe vibrations, it is necessary to do inspection on the bearings in the Amurang Unit 1 Power Plant.

  13. 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.

  14. 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).

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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....

  5. 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

  6. Anti vibration bars replacement in Vandellos II steam generators

    International Nuclear Information System (INIS)

    Vinyes, R.; Leal, R.

    1994-01-01

    C.N. Vandellos II is equipped with three steam generators Westinghouse model F. The number of tubes is 5626 each SG and the material Inconel 600TT. During the first inservice inspection, in 1989, tube wall thickness reductions were observed due to fretting in zones of contact with the tubes anti vibration bars. In the 2 nd shutdown for refueling (1990) all the tubes subject to this type of degradation were inspected by eddy currents, occurring a significative increase in number of tubes affected as well as the quantity of plugged tubes for that reason. Additionally, Westinghouse performed visual inspection and dimensional control of gaps in the tube bundles. Taking in account the results, the replacement with AVBs of new design was decided. AVBs new design is more complex than the original due to the combination of flexible and expandable bars in order to eliminate gaps between tubes an bars an assure proper bundle support. Given that the installation has to be done under water for shielding, all unions are bolted so that no welding is required. Each one of the bars, 333 per SG, is attached to a support structure consisting in 6 retaining plates and 4 bridge plates. (Author)

  7. ACO-Initialized Wavelet Neural Network for Vibration Fault Diagnosis of Hydroturbine Generating Unit

    Directory of Open Access Journals (Sweden)

    Zhihuai Xiao

    2015-01-01

    Full Text Available Considering the drawbacks of traditional wavelet neural network, such as low convergence speed and high sensitivity to initial parameters, an ant colony optimization- (ACO- initialized wavelet neural network is proposed in this paper for vibration fault diagnosis of a hydroturbine generating unit. In this method, parameters of the wavelet neural network are initialized by the ACO algorithm, and then the wavelet neural network is trained by the gradient descent algorithm. Amplitudes of the frequency components of the hydroturbine generating unit vibration signals are used as feature vectors for wavelet neural network training to realize mapping relationship from vibration features to fault types. A real vibration fault diagnosis case result of a hydroturbine generating unit shows that the proposed method has faster convergence speed and stronger generalization ability than the traditional wavelet neural network and ACO wavelet neural network. Thus it can provide an effective solution for online vibration fault diagnosis of a hydroturbine generating unit.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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...

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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.

  20. Torsional vibration analysis in turbo-generator shaft due to mal-synchronization fault

    Science.gov (United States)

    Bangunde, Abhishek; Kumar, Tarun; Kumar, Rajeev; Jain, S. C.

    2018-03-01

    A rotor of turbo-generator shafting is many times subjected to torsional vibrations during its lifespan. The reasons behind these vibrations are three-Phase fault, two-phase fault, line to ground fault, faulty-mal synchronization etc. Sometimes these vibrations can cause complete failure of turbo-generator shafting system. To calculate moment variation during these faults on the shafting system vibration analysis is done using Finite Elements Methods to calculate mass and stiffness matrix. The electrical disturbance caused during Mal-synchronization is put on generator section, and corresponding second order equations are solved by using “Duhamel Integral”. From the moment variation plots at four sections critically loaded sections are identified.

  1. Fluid induced structural vibrations in steam generators and heat exchangers

    International Nuclear Information System (INIS)

    Catton, I.; Adinolfi, P.; Alquaddoomi, O.

    2003-01-01

    Fluid-elastic instability (FEI) in tube bundle heat exchangers was studied experimentally. The motion of an array of 15 stainless steel vibrating tubes (Φ 25.4mm) in water cross-flow, suspended using stainless steel piano wire has been recorded with a CCD camera. The individual motion and relative motion of the tubes are reported and can be used for computational model validation. The relative displacement of the tubes allows identification of the most potentially damaging patterns of tube bundle vibration. A critical reduced velocity may be determined by specification of an allowable limit on tube motion amplitude. Measurements were made for various tube array configurations, tube natural frequencies and flow conditions. (author)

  2. 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.

  3. 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

  4. Detection of generator bearing inner race creep by means of vibration and temperature analysis

    DEFF Research Database (Denmark)

    Skrimpas, Georgios Alexandros; Dragiev, Ivaylo G.; Hilmisson, Reynir

    2015-01-01

    Vibration and temperature analysis are the two dominating condition monitoring techniques applied to fault detection of bearing failures in wind turbine generators. Relative movement between the bearing inner ring and generator axle is one of the most severe failure modes in terms of secondary...... damages and development. Detection of bearing creep can be achieved reliably based on continuous trending of the amplitude of vibration running speed harmonic and temperature absolute values. In order to decrease the number of condition indicators which need to be assessed, it is proposed to exploit...... a weighted average descriptor calculated based on the 3rd up to 6th harmonic orders. Two cases of different bearing creep severity are presented, showing the consistency of the combined vibration and temperature data utilization. In general, vibration monitoring reveals early signs of abnormality several...

  5. Research of hydroelectric generating set low-frequency vibration monitoring system based on optical fiber sensing

    Science.gov (United States)

    Min, Li; Zhang, Xiaolei; Zhang, Faxiang; Sun, Zhihui; Li, ShuJuan; Wang, Meng; Wang, Chang

    2017-10-01

    In order to satisfy hydroelectric generating set low-frequency vibration monitoring, the design of Passive low-frequency vibration monitoring system based on Optical fiber sensing in this paper. The hardware of the system adopts the passive optical fiber grating sensor and unbalanced-Michelson interferometer. The software system is used to programming by Labview software and finishing the control of system. The experiment show that this system has good performance on the standard vibration testing-platform and it meets system requirements. The frequency of the monitoring system can be as low as 0.2Hz and the resolution is 0.01Hz.

  6. 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.

  7. Validation of DIVA: an expert system for the diagnostic of turbo-generator vibrations

    International Nuclear Information System (INIS)

    Chevalier, R.; Ricard, B.; Tiarri, J.P.; Bonnet, J.C.

    1990-01-01

    The project presented in this paper concerns the development of an expert system dealing with the diagnosis of turbo-generator vibrations. DIVA - Diagnosis of Shaft Line Vibrations - is a joint project which is carried out by ALSTHOM, Electricite de France and Laboratoire de Marcoussis, research centre of CGE. This article first presents the organisation of the system and then the goals and results of the tests already achieved [fr

  8. 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.

  9. Atmospheric pressure reaction cell for operando sum frequency generation spectroscopy of ultrahigh vacuum grown model catalysts

    Science.gov (United States)

    Roiaz, Matteo; Pramhaas, Verena; Li, Xia; Rameshan, Christoph; Rupprechter, Günther

    2018-04-01

    A new custom-designed ultrahigh vacuum (UHV) chamber coupled to a UHV and atmospheric-pressure-compatible spectroscopic and catalytic reaction cell is described, which allows us to perform IR-vis sum frequency generation (SFG) vibrational spectroscopy during catalytic (kinetic) measurements. SFG spectroscopy is an exceptional tool to study vibrational properties of surface adsorbates under operando conditions, close to those of technical catalysis. This versatile setup allows performing surface science, SFG spectroscopy, catalysis, and electrochemical investigations on model systems, including single crystals, thin films, and deposited metal nanoparticles, under well-controlled conditions of gas composition, pressure, temperature, and potential. The UHV chamber enables us to prepare the model catalysts and to analyze their surface structure and composition by low energy electron diffraction and Auger electron spectroscopy, respectively. Thereafter, a sample transfer mechanism moves samples under UHV to the spectroscopic cell, avoiding air exposure. In the catalytic cell, SFG spectroscopy and catalytic tests (reactant/product analysis by mass spectrometry or gas chromatography) are performed simultaneously. A dedicated sample manipulation stage allows the model catalysts to be examined from LN2 temperature to 1273 K, with gaseous reactants in a pressure range from UHV to atmospheric. For post-reaction analysis, the SFG cell is rapidly evacuated and samples are transferred back to the UHV chamber. The capabilities of this new setup are demonstrated by benchmark results of CO adsorption on Pt and Pd(111) single crystal surfaces and of CO adsorption and oxidation on a ZrO2 supported Pt nanoparticle model catalyst grown by atomic layer deposition.

  10. High-precision and low-cost vibration generator for low-frequency calibration system

    Science.gov (United States)

    Li, Rui-Jun; Lei, Ying-Jun; Zhang, Lian-Sheng; Chang, Zhen-Xin; Fan, Kuang-Chao; Cheng, Zhen-Ying; Hu, Peng-Hao

    2018-03-01

    Low-frequency vibration is one of the harmful factors that affect the accuracy of micro-/nano-measuring machines because its amplitude is significantly small and it is very difficult to avoid. In this paper, a low-cost and high-precision vibration generator was developed to calibrate an optical accelerometer, which is self-designed to detect low-frequency vibration. A piezoelectric actuator is used as vibration exciter, a leaf spring made of beryllium copper is used as an elastic component, and a high-resolution, low-thermal-drift eddy current sensor is applied to investigate the vibrator’s performance. Experimental results demonstrate that the vibration generator can achieve steady output displacement with frequency range from 0.6 Hz to 50 Hz, an analytical displacement resolution of 3.1 nm and an acceleration range from 3.72 mm s-2 to 1935.41 mm s-2 with a relative standard deviation less than 1.79%. The effectiveness of the high-precision and low-cost vibration generator was verified by calibrating our optical accelerometer.

  11. 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.

  12. 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.

  13. 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.

  14. 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).

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Analysis of generator bearing vibration data for diagnosing rotor circuit malfunction in DFIGs

    DEFF Research Database (Denmark)

    Skrimpas, Georgios Alexandros; Sweeney, Christian W.; Jensen, Bogi Bech

    2014-01-01

    Doubly fed induction generators (DFIGs) are the most popular configuration met in the wind energy sector occu- pying approximately 65 % of the total market share. Condition monitoring of wind turbine generators is performed based on vibration data collected from accelerometers mounted on the drive....... In this paper generator bearing vibration signature for a DFIG under operation with one rotor phase coil open is analysed and presented. Further this failure mode is compared to rotor dynamics fault, such as rotational looseness, and the difference in signature is discussed. Vibration data from a multi...... end and non-drive end bearings, meeting the requirements of numerous turbine operators for condition based maintenance. In a DFIG the voltage applied to the rotor is controlled by a converter, where electric connection between the two is accom- plished by using slip rings. Improper connection between...

  2. 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

  3. 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.

  4. Detection and generation of first sound in4He by vibrating superleak transducers

    Science.gov (United States)

    Giordano, N.; Edison, N.

    1986-07-01

    Measurement is made of the first-sound generation and detection efficiencies of vibrating superleak transducers (VSTs) operated in superfluid4He. This is accomplished by using an ordinary pressure transducer to generate first sound with a VST as the detector, and by using a pressure transducer to detect the sound generated by a VST. The results are in reasonably good agreement with the current theory of VST operation.

  5. Detection and generation of first sound in 4He by vibrating superleak transducers

    International Nuclear Information System (INIS)

    Giordano, N.; Edison, N.

    1986-01-01

    Measurement is made of the first-sound generation and detection efficiencies of vibrating superleak transducers (VSTs) operated in superfluid 4 He. This is accomplished by using an ordinary pressure transducer to generate first sound with a VST as the detector, and by using a pressure transducer to detect the sound generated by a VST. The results are in reasonably good agreement with the current theory of VST operation

  6. 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)

  7. Viscoelasticity of new generation thermoplastic polyurethane vibration isolators

    Science.gov (United States)

    Bek, Marko; Betjes, Joris; von Bernstorff, Bernd-Steffen; Emri, Igor

    2017-12-01

    This paper presents the analysis of pressure dependence of three thermoplastic polyurethane (TPU) materials on vibration isolation. The three TPU Elastollan® materials are 1190A, 1175A, and 1195D. The aim of this investigation was to analyze how much the performance of isolation can be enhanced using patented Dissipative bulk and granular systems technology. The technology uses granular polymeric materials to enhance materials properties (without changing its chemical or molecular composition) by exposing them to "self-pressurization," which shifts material energy absorption maxima toward lower frequencies, to match the excitation frequency of dynamic loading to which a mechanical system is exposed. Relaxation experiments on materials were performed at different isobaric and isothermal states to construct mastercurves, the time-temperature-pressure interrelation was modeled using the Fillers-Moonan-Tschoegl model. Dynamic material functions, related to isolation stiffness and energy absorption, were determined with the Schwarzl approximation. An increase in stiffness and energy absorption at selected hydrostatic pressure, compared to its stiffness and energy absorption at ambient conditions, is represented with κk(p, ω), defining the increase in stiffness and κd(p, ω), defining the increase in energy absorption. The study showed that close to the glassy state, moduli of 1190A and 1195D are about 6-9 times higher compared to 1175A, whereas their properties at ambient conditions are, for all practical purposes, the same. TPU 1190A turns out to be most sensitive to pressure: at 300 MPa its properties are shifted for 5.5 decades, while for 1195D and 1175A this shift is only 3.5 and 1.5 decades, respectively. In conclusion, the stiffness and energy absorption of isolation may be increased with pressure for about 100 times for 1190A and 1195D and for about 10 times for 1175A.

  8. Energy conversion by ‘T-shaped’ cantilever type electromagnetic vibration based micro power generator from low frequency vibration sources

    International Nuclear Information System (INIS)

    Siddique, Abu Raihan Mohammad; Mahmud, Shohel; Van Heyst, Bill

    2017-01-01

    Highlights: • A T-shaped cantilever type electromagnetic vibration based MPG has been described. • The designed EVMPG is useful for low frequency based vibration sources. • Both experimental tests and theoretical analysis have been performed. • The final compact prototype was tested at different conditions of human movements. • The prototype can generate 35.2 mV and 0.22 mW at 7 Hz with 5.6 Ω. - Abstract: The design, development, and analyses of low-frequency vibration based T-shaped cantilever type electromagnetic micro power generators (EVMPGs) are presented in this paper. Four different configurations (Configurations A to D) of EVMPGs were designed and fabricated and subsequently characterized using detailed experimental and limited analytical techniques. Configuration A and B consisted of a single and a double cylindrical moving magnets (NdFeB), respectively, while Configuration C consisted of four rectangular moving magnets with respect to a fixed copper coil. In contrast, Configuration D used a moving coil between four rectangular magnets with a back-iron bar. The open circuit RMS voltage output was observed to be a maximum from Configuration D (98.2 mV at 6.29 Hz) with a base vibration acceleration of 0.8 m s"−"2. Therefore, Configuration D was selected for further experimental investigations, which included changing the back-iron bar thickness, changing the base acceleration level, and changing the air gap separation between the magnets in order to optimize this configuration. The maximum load RMS voltage and power outputs of Configuration D were 105.4 mV and 1.35 mW at 6.29 Hz for load resistance 8.2 Ω and a base acceleration of 0.8 m s"−"2 with a 4.2 mm back-iron bar when the air gap between the magnets was 20 mm. Finally, a small portable EVMPG prototype was developed based on the Configuration D and was tested at different human movement conditions (i.e., walking, quick walking, and running). The developed EVMPG prototype was capable of

  9. 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.

  10. Femtosecond Coherent Anti-Stokes Raman Spectroscopy (CARS) As Next Generation Nonlinear LIDAR Spectroscopy and Microscopy

    International Nuclear Information System (INIS)

    Ooi, C. H. Raymond

    2009-01-01

    Nonlinear spectroscopy using coherent anti-Stokes Raman scattering and femtosecond laser pulses has been successfully developed as powerful tools for chemical analysis and biological imaging. Recent developments show promising possibilities of incorporating CARS into LIDAR system for remote detection of molecular species in airborne particles. The corresponding theory is being developed to describe nonlinear scattering of a mesoscopic particle composed of complex molecules by laser pulses with arbitrary shape and spectral content. Microscopic many-body transform theory is used to compute the third order susceptibility for CARS in molecules with known absorption spectrum and vibrational modes. The theory is combined with an integral scattering formula and Mie-Lorentz formulae, giving a rigorous formalism which provides powerful numerical experimentation of CARS spectra, particularly on the variations with the laser parameters and the direction of detection.

  11. 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].

  12. 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.

  13. Analysis Tools for Next-Generation Hadron Spectroscopy Experiments

    Science.gov (United States)

    Battaglieri, M.; Briscoe, B. J.; Celentano, A.; Chung, S.-U.; D'Angelo, A.; De Vita, R.; Döring, M.; Dudek, J.; Eidelman, S.; Fegan, S.; Ferretti, J.; Filippi, A.; Fox, G.; Galata, G.; García-Tecocoatzi, H.; Glazier, D. I.; Grube, B.; Hanhart, C.; Hoferichter, M.; Hughes, S. M.; Ireland, D. G.; Ketzer, B.; Klein, F. J.; Kubis, B.; Liu, B.; Masjuan, P.; Mathieu, V.; McKinnon, B.; Mitchel, R.; Nerling, F.; Paul, S.; Peláez, J. R.; Rademacker, J.; Rizzo, A.; Salgado, C.; Santopinto, E.; Sarantsev, A. V.; Sato, T.; Schlüter, T.; [Silva]da Silva, M. L. L.; Stankovic, I.; Strakovsky, I.; Szczepaniak, A.; Vassallo, A.; Walford, N. K.; Watts, D. P.; Zana, L.

    The series of workshops on New Partial-Wave Analysis Tools for Next-Generation Hadron Spectroscopy Experiments was initiated with the ATHOS 2012 meeting, which took place in Camogli, Italy, June 20-22, 2012. It was followed by ATHOS 2013 in Kloster Seeon near Munich, Germany, May 21-24, 2013. The third, ATHOS3, meeting is planned for April 13-17, 2015 at The George Washington University Virginia Science and Technology Campus, USA. The workshops focus on the development of amplitude analysis tools for meson and baryon spectroscopy, and complement other programs in hadron spectroscopy organized in the recent past including the INT-JLab Workshop on Hadron Spectroscopy in Seattle in 2009, the International Workshop on Amplitude Analysis in Hadron Spectroscopy at the ECT*-Trento in 2011, the School on Amplitude Analysis in Modern Physics in Bad Honnef in 2011, the Jefferson Lab Advanced Study Institute Summer School in 2012, and the School on Concepts of Modern Amplitude Analysis Techniques in Flecken-Zechlin near Berlin in September 2013. The aim of this document is to summarize the discussions that took place at the ATHOS 2012 and ATHOS 2013 meetings. We do not attempt a comprehensive review of the field of amplitude analysis, but offer a collection of thoughts that we hope may lay the ground for such a document.

  14. Analysis Tools for Next-Generation Hadron Spectroscopy Experiments

    International Nuclear Information System (INIS)

    Battaglieri, Marco; Briscoe, William; Celentano, Andrea; Chung, Suh-Urk; D'Angelo, Annalisa; De Vita, Rafaella; Döring, Michael; Dudek, Jozef; Eidelman, S.; Fegan, Stuart; Ferretti, J.; Filippi, A.; Fox, G.; Galata, G.; Garcia-Tecocoatzi, H.; Glazier, Derek; Grube, B.; Hanhart, C.; Hoferichter, M.; Hughes, S. M.; Ireland, David G.; Ketzer, B.; Klein, Franz J.; Kubis, B.; Liu, B.; Masjuan, P.; Mathieu, Vincent; McKinnon, Brian; Mitchel, R.; Nerling, F.; Paul, S.; Peláez, J. R.; Rademacker, J.; Rizzo, Alessandro; Salgado, Carlos; Santopinto, E.; Sarantsev, Andrey V.; Sato, Toru; Schlüter, T.; Da Silva, M. L.L.; Stankovic, I.; Strakovsky, Igor; Szczepaniak, Adam; Vassallo, A.; Walford, Natalie K.; Watts, Daniel P.

    2015-01-01

    The series of workshops on New Partial-Wave Analysis Tools for Next-Generation Hadron Spectroscopy Experiments was initiated with the ATHOS 2012 meeting, which took place in Camogli, Italy, June 20-22, 2012. It was followed by ATHOS 2013 in Kloster Seeon near Munich, Germany, May 21-24, 2013. The third, ATHOS3, meeting is planned for April 13-17, 2015 at The George Washington University Virginia Science and Technology Campus, USA. The workshops focus on the development of amplitude analysis tools for meson and baryon spectroscopy, and complement other programs in hadron spectroscopy organized in the recent past including the INT-JLab Workshop on Hadron Spectroscopy in Seattle in 2009, the International Workshop on Amplitude Analysis in Hadron Spectroscopy at the ECT*-Trento in 2011, the School on Amplitude Analysis in Modern Physics in Bad Honnef in 2011, the Jefferson Lab Advanced Study Institute Summer School in 2012, and the School on Concepts of Modern Amplitude Analysis Techniques in Flecken-Zechlin near Berlin in September 2013. The aim of this document is to summarize the discussions that took place at the ATHOS 2012 and ATHOS 2013 meetings. We do not attempt a comprehensive review of the field of amplitude analysis, but offer a collection of thoughts that we hope may lay the ground for such a document

  15. 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.

  16. 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.

  17. 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.

  18. Flow-induced vibration analysis of heat exchanger and steam generator designs

    International Nuclear Information System (INIS)

    Pettigrew, M.J.; Sylvestre, Y.; Campagna, A.O.

    1977-08-01

    Tube and shell heat exchange components such as steam generators, heat exchangers and condensers are essential parts of CANDU nuclear power stations. Excessive flow-induced vibration may cause tube failures by fatigue or more likely by fretting-wear. Such failures may lead to station shutdowns that are very undesirable in terms of lost production. Hence good performance and reliability dictate a thorough flow-induced vibration analysis at the design stage. This paper presents our approach and techniques in this respect. (author)

  19. Generation of narrow peaks in spectroscopy of charged particles

    Energy Technology Data Exchange (ETDEWEB)

    Dubbers, Dirk, E-mail: dubbers@physi.uni-heidelberg.de; Schmidt, Ulrich, E-mail: ulrich.schmidt@physi.uni-heidelberg.de

    2016-11-21

    In spectroscopy of charged particles, narrow peaks may appear in continuous spectra if magnetic transport of the particles is involved. These artefacts, which so far have escaped the attention of investigators, can develop whenever geometric detection efficiency is less than 100%. As such peaks may be misinterpreted as new physics, their generation is investigated, both analytically and experimentally, for various detector configurations, including those used in searches for the spontaneous decay of the vacuum in heavy-ion collisions.

  20. Vibration and wear prediction for steam generator tubes: Final report

    International Nuclear Information System (INIS)

    Rao, M.S.M.; Gupta, G.D.; Eisinger, F.L.

    1988-06-01

    As part of the overall EPRI program to develop a mechanistic model for tube fretting and wear prediction, Foster Wheeler Development Corporation undertook the responsibility of developing analytical models to predict structural response and wear in a multispan tube. The project objective was to develop the analytical capability to simulate the time-dependent motion of a multispan steam generator tube in the presence of the clearance gaps at each tube baffle or support. The models developed were to simulate nonlinear tube-to-tube support interaction by determining the impact force, the sliding distance, and the resultant tube wear. Other objectives of the project included: validate the models by comparing the analytical results with the EPRI tests done at Combustion Engineering (C-E) on single multispan tubes; test the models for simulating the U-bend region of the steam generator tube, including the antivibration bars; and develop simplified methods to treat the nonlinear dynamic problem of a multispan tube so that computing costs could be minimized. 15 refs., 53 figs., 27 tabs

  1. 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

  2. Two methods for damping torsional vibrations in DFIG-based wind generators using power converters

    Science.gov (United States)

    Zhao, Zuyi; Lu, Yupu; Xie, Da; Yu, Songtao; Wu, Wangping

    2017-01-01

    This paper proposes novel damping control algorithms by using static synchronous compensator (STATCOM) and energy storage system (ESS) to damp torsional vibrations in doubly fed induction generator (DFIG) based wind turbine systems. It first analyses the operating characteristics of STATCOM and ESS for regulating power variations to increase grid voltage stability. Then, new control strategies for STATCOM and ESS are introduced to damp the vibrations. It is followed by illustration of their effectiveness to damp the drive train torsional vibrations of wind turbines, which can be caused by grid disturbances, such as voltage sags and frequency fluctuations. Results suggest that STATCOM is a promising technology to mitigate the torsional vibrations caused by grid voltage sags. By contrast, the ESS connected to the point of common coupling (PCC) of wind turbine systems shows even obvious advantages because of its capability of absorbing/releasing both active and reactive power. It can thus be concluded that STATCOM is useful for stabilizing power system voltage fluctuations, and ESS is more effective both in regulating PCC voltage fluctuations and damping torsional vibrations caused by grid voltage frequency fluctuations.

  3. 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

  4. 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

  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. 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.

  8. 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.

  9. 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.

  10. Improvement of force factor of magnetostrictive vibration power generator for high efficiency

    International Nuclear Information System (INIS)

    Kita, Shota; Ueno, Toshiyuki; Yamada, Sotoshi

    2015-01-01

    We develop high power magnetostrictive vibration power generator for battery-free wireless electronics. The generator is based on a cantilever of parallel beam structure consisting of coil-wound Galfenol and stainless plates with permanent magnet for bias. Oscillating force exerted on the tip bends the cantilever in vibration yields stress variation of Galfenol plate, which causes flux variation and generates voltage on coil due to the law of induction. This generator has advantages over conventional, such as piezoelectric or moving magnet types, in the point of high efficiency, highly robust, and low electrical impedance. Our concern is the improvement of energy conversion efficiency dependent on the dimension. Especially, force factor, the conversion ratio of the electromotive force (voltage) on the tip velocity in vibration, has an important role in energy conversion process. First, the theoretical value of the force factor is formulated and then the validity was verified by experiments, where we compare four types of prototype with parameters of the dimension using 7.0 × 1.5 × 50 mm beams of Galfenol with 1606-turn wound coil. In addition, the energy conversion efficiency of the prototypes depending on load resistance was measured. The most efficient prototype exhibits the maximum instantaneous power of 0.73 W and energy of 4.7 mJ at a free vibration of frequency of 202 Hz in the case of applied force is 25 N. Further, it was found that energy conversion efficiency depends not only on the force factor but also on the damping (mechanical loss) of the vibration

  11. Nonlinear optical response of a gold surface in the visible range: A study by two-color sum-frequency generation spectroscopy. I. Experimental determination.

    Science.gov (United States)

    Dalstein, L; Revel, A; Humbert, C; Busson, B

    2018-04-07

    We experimentally determine the effective nonlinear second-order susceptibility of gold over the visible spectral range. To reach that goal, we probe by vibrational two-color sum-frequency generation spectroscopy the methyl stretching region of a dodecanethiol self-assembled monolayer adsorbed on a gold film. The sum-frequency generation spectra show a remarkable shape reversal when the visible probe wavelength is tuned from 435 to 705 nm. After correcting from Fresnel effects, the methyl stretching vibrations serve as an internal reference, allowing to extract the dispersion of the absolute phase and relative amplitude of the effective nonlinear optical response of gold in the visible range.

  12. 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

  13. 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.

  14. Condition monitoring of steam turbo generators of captive power plant at HWP (Manuguru) through vibration analysis

    International Nuclear Information System (INIS)

    Krishnareddy, G.; Chandramouli, M.; Gupta, R.V.

    2002-01-01

    Turbo Generator is a critical equipment in steam based power plant circuit. Any failure causes loss of production and hence as applicable to Heavy Water Plant, Manuguru, it results in loss of heavy water production as the captive power plant at Manuguru is solely designed to supply steam and power to Main Plant, which is meant for production of heavy water. Thereby condition monitoring is very much essential and required as part of predictive maintenance program for the turbo generators which are in continuous operation. This paper focuses on identification of the turbo generator system through vibration spectrum, characterising and differentiating the fault mechanisms, trending the faults through changes in vibration spectrums and orbit plots and subsequently planning for corrective actions/measures after evaluating the changes in machine conditions

  15. Anisotropic Formation of Quantum Turbulence Generated by a Vibrating Wire in Superfluid {}4{He}

    Science.gov (United States)

    Yano, H.; Ogawa, K.; Chiba, Y.; Obara, K.; Ishikawa, O.

    2017-06-01

    To investigate the formation of quantum turbulence in superfluid {}4{He}, we have studied the emission of vortex rings with a ring size of larger than 38 μm in diameter from turbulence generated by a vibrating wire. The emission rate of vortex rings from a turbulent region remains low until the beginning of high-rate emissions, suggesting that some of the vortex lines produced by the wire combine to form a vortex tangle, until an equilibrium is established between the rate of vortex line combination with the tangle and dissociation. The formation times of equilibrium turbulence are proportional to ɛ ^{-1.2} and ɛ ^{-0.6} in the directions perpendicular and parallel to the vibrating direction of the generator, respectively, indicating the anisotropic formation of turbulence. Here, ɛ is the generation power of the turbulence. This power dependence may be associated with the characteristics of quantum turbulence with a constant energy flux.

  16. 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.

  17. 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

  18. 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

  19. 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...

  20. Effect of material constants on power output in piezoelectric vibration-based generators.

    Science.gov (United States)

    Takeda, Hiroaki; Mihara, Kensuke; Yoshimura, Tomohiro; Hoshina, Takuya; Tsurumi, Takaaki

    2011-09-01

    A possible power output estimation based on material constants in piezoelectric vibration-based generators is proposed. A modified equivalent circuit model of the generator was built and was validated by the measurement results in the generator fabricated using potassium sodium niobate-based and lead zirconate titanate (PZT) ceramics. Subsequently, generators with the same structure using other PZT-based and bismuth-layered structure ferroelectrics ceramics were fabricated and tested. The power outputs of these generators were expressed as a linear functions of the term composed of electromechanical coupling coefficients k(sys)(2) and mechanical quality factors Q*(m) of the generator. The relationship between device constants (k(sys)(2) and Q*(m)) and material constants (k(31)(2) and Q(m)) was clarified. Estimation of the power output using material constants is demonstrated and the appropriate piezoelectric material for the generator is suggested.

  1. Free vibration analysis of a steam generator tube bundle with and without lateral support

    International Nuclear Information System (INIS)

    King, D.M.

    1979-04-01

    The vibrational modes and frequency characteristics of a pressurized water reactor (PWR) steam generator tube bundle assembly with and without lateral support in a fluid environment are analyzed. The idealized half-model was constructed using the SAP-IV finite element code. Free vibration analyses were performed for an in-air case and a submerged in-water case, each with different constraint conditions at steam generator tube bundle assembly support plates 10 and 11. These constraint conditions included having both support plates free, having both support plates fixed, and having support plate 11 free while support plate 10 was fixed. It was found that as the support plate constraints were removed, the frequency range for each case increased significantly

  2. Distributed optical fiber vibration sensing using phase-generated carrier demodulation algorithm

    Science.gov (United States)

    Yu, Zhihua; Zhang, Qi; Zhang, Mingyu; Dai, Haolong; Zhang, Jingjing; Liu, Li; Zhang, Lijun; Jin, Xing; Wang, Gaifang; Qi, Guang

    2018-05-01

    A novel optical fiber-distributed vibration-sensing system is proposed, which is based on self-interference of Rayleigh backscattering with phase-generated carrier (PGC) demodulation algorithm. Pulsed lights are sent into the sensing fiber and the Rayleigh backscattering light from a certain position along the sensing fiber would interfere through an unbalanced Michelson interferometry to generate the interference light. An improved PGC demodulation algorithm is carried out to recover the phase information of the interference signal, which carries the sensing information. Three vibration events were applied simultaneously to different positions over 2000 m sensing fiber and demodulated correctly. The spatial resolution is 10 m, and the noise level of the Φ-OTDR system we proposed is about 10-3 rad/\\surd {Hz}, and the signal-to-noise ratio is about 30.34 dB.

  3. Second harmonic generation spectroscopy on Si surfaces and interfaces

    DEFF Research Database (Denmark)

    Pedersen, Kjeld

    2010-01-01

    Optical second harmonic generation (SHG) spectroscopy studies of Si(111) surfaces and interfaces are reviewed for two types of systems: (1) clean 7 x 7 and root 3 x root 3-Ag reconstructed surfaces prepared under ultra-high vacuum conditions where surface states are excited and (2) interfaces...... in silicon-on-insulator (SOI) structures and thin metal films on Si surfaces where several interfaces contribute to the SHG. In all the systems resonances are seen at interband transitions near the bulk critical points E-1 and E-2. On the clean surfaces a number of resonances appear below the onset of bulk...

  4. Lateral Vibration of Hydroelectric Generating Set with Different Supporting Condition of Thrust Pad

    OpenAIRE

    Si, Xiaohui; Lu, Wenxiu; Chu, Fulei

    2011-01-01

    The variations of the supporting condition, which change the stiffness of tilting pad thrust bearing, may alter the dynamic behavior of the rotor system. The effects of supporting condition of thrust pad on the lateral vibration of a hydroelectric generating set are investigated in this paper. The action of a thrust bearing is described as moments acting on the thrust collar, and the tilting stiffness coefficients of thrust bearing are calculated. A model based on typical beam finite element ...

  5. ACO-Initialized Wavelet Neural Network for Vibration Fault Diagnosis of Hydroturbine Generating Unit

    OpenAIRE

    Xiao, Zhihuai; He, Xinying; Fu, Xiangqian; Malik, O. P.

    2015-01-01

    Considering the drawbacks of traditional wavelet neural network, such as low convergence speed and high sensitivity to initial parameters, an ant colony optimization- (ACO-) initialized wavelet neural network is proposed in this paper for vibration fault diagnosis of a hydroturbine generating unit. In this method, parameters of the wavelet neural network are initialized by the ACO algorithm, and then the wavelet neural network is trained by the gradient descent algorithm. Amplitudes of the fr...

  6. Vibration Energy Harvesting on Vehicle Suspension Using Rotary and Linear Electromagnetic Generator

    Directory of Open Access Journals (Sweden)

    Arif Indro Sultoni

    2013-04-01

    Full Text Available In this paper, we discuss comparation of vehicle vibration energy harvesting between rotary and linear electromagnetic generator. We construct the two model of energy harvester mechanism and then analyze both of energy absorbtion and vehicle comfortability. Furthermore, we analyze both of energy absorbtion and vehicle comfortability. Vehicle is modeled as quarter car. Rotarty generator harvests 2.5 x 10-4 Watt. The other hand, linear generator has viscous characteristic and capable to generates 90 Watts with 12 Volt power supply for 0.03 m amplitude of bumpy road input. Linear generator reduces oscillation with 1.2 sec settling time. It is more comfort than the angular which has 3 sec in settling time. With unnevenees road input, mean power of this generator is 64 Watt.

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. Simultaneous rotational and vibrational CARS generation through a multiple-frequency combination technique

    International Nuclear Information System (INIS)

    Alden, M.; Bengtsson, P.E.; Edner, H.

    1987-01-01

    One most promising laser technique for probing combustion processes is coherent anti-Stokes Raman scattering (CARS), which due to its coherent nature and signal strength is applied in several real-world applications. Until today almost all CARS experiments are based on probing the population of molecular vibrational energy levels. However, there are several reasons rotational CARS, i.e. probing of rotational energy levels, may provide a complement to or even a better choice than vibrational CARS. Recently an alternative way to produce rotational CARS spectra is proposed, which is based on a multiple-frequency combination technique. The energy-level diagram for this process is presented. Two dye laser beams at ω/sub r/, and one fix frequency laser beam at ω/sub g/ are employed. ω/sub r,1/ and ω/sub r,2/ are two frequencies of many possible pairs with a frequency difference matching a rotational transition in a molecule. The excitation induced by ω/sub r,1/ and ω/sub r,2/ is then scattered by the narrowband ω/sub g/ beam resulting in a CARS beam ω/sub g/ at ω/sub g/ + ω/sub r,1/ - ω/sub r,2/. An interesting feature with this technique is that it is possible to generate simultaneously a rotational and vibrational CARS spectrum by using a double-folded boxcars phase matching approach. The authors believe that the proposed technique for producing rotational and vibration CARS spectra could be of interest, e.g., when measuring in highly turbulent flows. In this case the rotational CARS spectra could use for temperature measurements in the cooler parts, whereas vibrational CARS are to be preferred when measuring in the hotter parts

  13. Flow-induced vibration analysis of a helical coil steam generator experiment using large eddy simulation

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Haomin; Solberg, Jerome; Merzari, Elia; Kraus, Adam; Grindeanu, Iulian

    2017-10-01

    This paper describes a numerical study of flow-induced vibration in a helical coil steam generator experiment conducted at Argonne National Laboratory in the 1980s. In the experiment, a half-scale sector model of a steam generator helical coil tube bank was subjected to still and flowing air and water, and the vibrational characteristics were recorded. The research detailed in this document utilizes the multi-physics simulation toolkit SHARP developed at Argonne National Laboratory, in cooperation with Lawrence Livermore National Laboratory, to simulate the experiment. SHARP uses the spectral element code Nek5000 for fluid dynamics analysis and the finite element code DIABLO for structural analysis. The flow around the coil tubes is modeled in Nek5000 by using a large eddy simulation turbulence model. Transient pressure data on the tube surfaces is sampled and transferred to DIABLO for the structural simulation. The structural response is simulated in DIABLO via an implicit time-marching algorithm and a combination of continuum elements and structural shells. Tube vibration data (acceleration and frequency) are sampled and compared with the experimental data. Currently, only one-way coupling is used, which means that pressure loads from the fluid simulation are transferred to the structural simulation but the resulting structural displacements are not fed back to the fluid simulation

  14. The vibrational behaviour of the generator support structure for Koeberg nuclear power station at high frequencies

    International Nuclear Information System (INIS)

    Lee, D.E.

    1988-06-01

    The vibrational behaviour of the generator support structure at Koeberg nuclear power station at frequencies primarily in the region of 80 Hz to 110 Hz was examined. The effect of soil-structure interaction and the change in stiffness of the foundation soil was investigated. Vibration tests were performed on the generator support structure and the results were compared with a theoretical finite element analysis of the structure. By varying the soil-cement foundation stiffness it was possible to demonstrate the change in dynamic behaviour of the structure in the higher frequency band 80 Hz to 110 Hz. Comment has been made on the design code DIN 4024 in view of the findings of this thesis. It was concluded that the empirical rules regarding the inclusion of the foundation in an analysis specified by the code do not cover all cases and greater cognisance of the effect of the foundation stiffness on the vibration behaviour of such machine foundations is necessary. Obvious machine frequencies higher than the operational frequencies should be analysed where it is considered necessary. 24 refs., 25 tabs., 83 figs

  15. Over-the-road shock and vibration testing of the radioisotope thermoelectric generator transportation system

    International Nuclear Information System (INIS)

    Becker, D.L.

    1997-01-01

    Radioisotope Thermoelectric Generators (RTG) convert heat generated by radioactive decay into electricity through the use of thermocouples. The RTGs have a long operating life, are reasonably lightweight, and require little or no maintenance, which make them particularly attractive for use in spacecraft. However, because RTGs contain significant quantities of radioactive materials, normally plutonium-238 and its decay products, they must be transported in packages built in accordance with Title 10, Code of Federal Regulations, Part 71 (10 CFR 71). To meet these regulations, a RTG Transportation System (RTGTS) that fully complies with 10 CFR 71 has been developed, which protects RTGs from adverse environmental conditions during normal conditions of transport (e.g., shock, vibration, and heat). To ensure the protection of RTGs from shock and vibration loadings during transport, extensive over-the-road testing was conducted on the RTG'S to obtain real-time recordings of accelerations of the air-ride suspension system trailer floor, packaging, and support structure. This paper provides an overview of the RTG'S, a discussion of the shock and vibration testing, and a comparison of the test results to the specified shock response spectra and power spectral density acceleration criteria

  16. Vibrational excitation of hydrogen molecules by two-photon absorption and third-harmonic generation

    Science.gov (United States)

    Miyamoto, Yuki; Hara, Hideaki; Hiraki, Takahiro; Masuda, Takahiko; Sasao, Noboru; Uetake, Satoshi; Yoshimi, Akihiro; Yoshimura, Koji; Yoshimura, Motohiko

    2018-01-01

    We report the coherent excitation of the vibrational state of hydrogen molecules by two-photon absorption and the resultant third-harmonic generation (THG). Parahydrogen molecules cooled by liquid nitrogen are irradiated by mid-infrared nanosecond pulses at 4.8 μm with a nearly Fourier-transform-limited linewidth. The first excited vibrational state of parahydrogen is populated by two-photon absorption of the mid-infrared photons. Because of the narrow linewidth of the mid-infrared pulses, coherence between the ground and excited states is sufficient to induce higher-order processes. Near-infrared photons from the THG are observed at 1.6 μm. The dependence of the intensity of the near-infrared radiation on mid-infrared pulse energy, target pressure, and cell length is determined. We used a simple formula for THG with consideration of realistic experimental conditions to explain the observed results.

  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. Development of Design Criteria for Fluid Induced Structural Vibrations in Steam Generators and Heat Exchangers

    International Nuclear Information System (INIS)

    Catton, Ivan; Dhir, Vijay K.; Alquaddoomi, O.S.; Mitra, Deepanjan; Adinolfi, Pierangelo

    2004-01-01

    OAK-B135 Flow-induced vibration in heat exchangers has been a major cause of concern in the nuclear industry for several decades. Many incidents of failure of heat exchangers due to apparent flow-induced vibration have been reported through the USNRC incident reporting system. Almost all heat exchangers have to deal with this problem during their operation. The phenomenon has been studied since the 1970s and the database of experimental studies on flow-induced vibration is constantly updated with new findings and improved design criteria for heat exchangers. In the nuclear industry, steam generators are often affected by this problem. However, flow-induced vibration is not limited to nuclear power plants, but to any type of heat exchanger used in many industrial applications such as chemical processing, refrigeration and air conditioning. Specifically, shell and tube type heat exchangers experience flow-induced vibration due to the high velocity flow over the tube banks. Flow-induced vibration in these heat exchangers leads to equipment breakdown and hence expensive repair and process shutdown. The goal of this research is to provide accurate measurements that can help modelers to validate their models using the measured experimental parameters and thereby develop better design criteria for avoiding fluid-elastic instability in heat exchangers. The research is divided between two primary experimental efforts, the first conducted using water alone (single phase) and the second using a mixture of air or steam and water as the working fluid (two phase). The outline of this report is as follows: After the introduction to fluid-elastic instability, the experimental apparatus constructed to conduct the experiments is described in Chapter 2 along with the measurement procedures. Chapter 3 presents results obtained on the tube array and the flow loop, as well as techniques used in data processing. The project performance is described and evaluated in Chapter 4 followed by

  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. Dynamics and Control of Lateral Tower Vibrations in Offshore Wind Turbines by Means of Active Generator Torque

    Directory of Open Access Journals (Sweden)

    Zili Zhang

    2014-11-01

    Full Text Available Lateral tower vibrations of offshore wind turbines are normally lightly damped, and large amplitude vibrations induced by wind and wave loads in this direction may significantly shorten the fatigue life of the tower. This paper proposes the modeling and control of lateral tower vibrations in offshore wind turbines using active generator torque. To implement the active control algorithm, both the mechanical and power electronic aspects have been taken into consideration. A 13-degrees-of-freedom aeroelastic wind turbine model with generator and pitch controllers is derived using the Euler–Lagrangian approach. The model displays important features of wind turbines, such as mixed moving frame and fixed frame-defined degrees-of-freedom, couplings of the tower-blade-drivetrain vibrations, as well as aerodynamic damping present in different modes of motions. The load transfer mechanisms from the drivetrain and the generator to the nacelle are derived, and the interaction between the generator torque and the lateral tower vibration are presented in a generalized manner. A three-dimensional rotational sampled turbulence field is generated and applied to the rotor, and the tower is excited by a first order wave load in the lateral direction. Next, a simple active control algorithm is proposed based on active generator torques with feedback from the measured lateral tower vibrations. A full-scale power converter configuration with a cascaded loop control structure is also introduced to produce the feedback control torque in real time. Numerical simulations have been carried out using data calibrated to the referential 5-MW NREL (National Renewable Energy Laboratory offshore wind turbine. Cases of drivetrains with a gearbox and direct drive to the generator are considered using the same time series for the wave and turbulence loadings. Results show that by using active generator torque control, lateral tower vibrations can be significantly mitigated for

  4. Note: A simple vibrating orifice monodisperse droplet generator using a hard drive actuator arm

    Energy Technology Data Exchange (ETDEWEB)

    Kosch, Sebastian, E-mail: skosch@mie.utoronto.ca, E-mail: ashgriz@mie.utoronto.ca; Ashgriz, Nasser, E-mail: skosch@mie.utoronto.ca, E-mail: ashgriz@mie.utoronto.ca [Department of Industrial and Mechanical Engineering, University of Toronto, Toronto, Ontario M5S 3G8 (Canada)

    2015-04-15

    We propose that the rotary voice coil actuators found in magnetic hard drives are fit to supercede loudspeakers as expedient vibration sources in the laboratory setting. A specific use case is the excitation of a liquid jet to induce controlled breakup into monodisperse droplets. Like loudspeakers, which are typically used for prototyping such devices, hard drive actuators are cheap and ubiquitous, but they are less unwieldy and supply greater amplitudes without producing noise. Frequencies between 0 and 17 kHz, and likely beyond, can be reproduced reliably. No machining tools or amplifying electronics are needed for the construction and operation of the presented droplet generator.

  5. Vibration characteristics of a hydraulic generator unit rotor system with parallel misalignment and rub-impact

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhiwei; Zhou, Jianzhong; Yang, Mengqi; Zhang, Yongchuan [Huazhong University of Science and Technology, College of Hydraulic and Digitalization Engineering, Wuhan, Hubei Province (China)

    2011-07-15

    The object of this research aims at the hydraulic generator unit rotor system. According to fault problems of the generator rotor local rubbing caused by the parallel misalignment and mass eccentricity, a dynamic model for the rotor system coupled with misalignment and rub-impact is established. The dynamic behaviors of this system are investigated using numerical integral method, as the parallel misalignment, mass eccentricity and bearing stiffness vary. The nonlinear dynamic responses of the generator rotor and turbine rotor with coupling faults are analyzed by means of bifurcation diagrams, Poincare maps, axis orbits, time histories and amplitude spectrum diagrams. Various nonlinear phenomena in the system, such as periodic, three-periodic and quasi-periodic motions, are studied with the change of the parallel misalignment. The results reveal that vibration characteristics of the rotor system with coupling faults are extremely complex and there are some low frequencies with large amplitude in the 0.3-0.4 x components. As the increase in mass eccentricity, the interval of nonperiodic motions will be continuously moved forward. It suggests that the reduction in mass eccentricity or increase in bearing stiffness could preclude nonlinear vibration. These might provide some important theory references for safety operating and exact identification of the faults in rotating machinery. (orig.)

  6. Pairing vibrational and isospin rotational states in a particle number and isospin projected generator coordinate method

    International Nuclear Information System (INIS)

    Chen, H.T.; Muether, H.; Faessler, A.

    1978-01-01

    Pairing vibrational and isospin rotational states are described in different approximations based on particle number and isospin projected, proton-proton, neutron-neutron and proton-neutron pairing wave functions and on the generator coordinate method (GCM). The investigations are performed in models for which an exact group theoretical solution exists. It turns out that a particle number and isospin projection is essential to yield a good approximation to the ground state or isospin yrast state energies. For strong pairing correlations (pairing force constant equal to the single-particle level distance) isospin cranking (-ωTsub(x)) yields with particle number projected pairing wave function also good agreement with the exact energies. GCM wave functions generated by particle number and isospin projected BCS functions with different amounts of pairing correlations yield for the lowest T=0 and T=2 states energies which are practically indistinguishable from the exact solutions. But even the second and third lowest energies of charge-symmetric states are still very reliable. Thus it is concluded that also in realistic cases isospin rotational and pairing vibrational states may be described in the framework of the GCM method with isospin and particle number projected generating wave functions. (Auth.)

  7. 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

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. An advanced tube wear and fatigue workstation to predict flow induced vibrations of steam generator tubes

    International Nuclear Information System (INIS)

    Gay, N.; Baratte, C.; Flesch, B.

    1997-01-01

    Flow induced tube vibration damage is a major concern for designers and operators of nuclear power plant steam generators (SG). The operating flow-induced vibrational behaviour has to be estimated accurately to allow a precise evaluation of the new safety margins in order to optimize the maintenance policy. For this purpose, an industrial 'Tube Wear and Fatigue Workstation', called 'GEVIBUS Workstation' and based on an advanced methodology for predictive analysis of flow-induced vibration of tube bundles subject to cross-flow has been developed at Electricite de France. The GEVIBUS Workstation is an interactive processor linking modules as: thermalhydraulic computation, parametric finite element builder, interface between finite element model, thermalhydraulic code and vibratory response computations, refining modelling of fluid-elastic and random forces, linear and non-linear dynamic response and the coupled fluid-structure system, evaluation of tube damage due to fatigue and wear, graphical outputs. Two practical applications are also presented in the paper; the first simulation refers to an experimental set-up consisting of a straight tube bundle subject to water cross-flow, while the second one deals with an industrial configuration which has been observed in some operating steam generators i.e., top tube support plate degradation. In the first case the GEVIBUS predictions in terms of tube displacement time histories and phase planes have been found in very good agreement with experiment. In the second application the GEVIBUS computation showed that a tube with localized degradation is much more stable than a tube located in an extended degradation zone. Important conclusions are also drawn concerning maintenance. (author)

  14. 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.

  15. Optimal linear generator with Halbach array for harvesting of vibration energy during human walking

    Directory of Open Access Journals (Sweden)

    Joonsoo Jun

    2016-05-01

    Full Text Available In IT business, the capacity of the battery in smartphone was drastically improved to digest various functions such as communication, Internet, e-banking, and entertainment. Although the capacity of the battery is improved, it still needs to be upgraded due to customer’s demands. In this article, we optimize the design of the linear generator with the Halbach array to improve the efficiency of harvesting vibration energy during human walking for the battery capacitance. We propose the optimal design of the tubular permanent magnet with the linear generator that uses a Halbach array. The approximate model is established using generic algorithm. Furthermore, we performed electromagnetic finite element analysis to predict the induced voltage.

  16. 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.

  17. 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

  18. Vibrational sum frequency generation (SFG) spectroscopic study of crystalline cellulose in biomass

    Science.gov (United States)

    Kim, Seong H.; Lee, Christopher M.; Kafle, Kabindra; Park, Yong Bum; Xi, Xiaoning

    2013-09-01

    The noncentrosymmetry requirement of sum frequency generation (SFG) spectroscopy allows selective detection of crystalline cellulose in plant cell walls and lignocellulose biomass without spectral interferences from hemicelluloses and lignin. In addition, the phase synchronization requirement of the SFG process allows noninvasive investigation of spatial arrangement of crystalline cellulose microfibrils in the sample. This paper reviews how these principles are applied to reveal structural information of crystalline cellulose in plant cell walls and biomass.

  19. 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.

  20. Sum frequency generation spectroscopy of tetraalkylphosphonium ionic liquids at the air-liquid interface

    Science.gov (United States)

    Peñalber-Johnstone, Chariz; Adamová, Gabriela; Plechkova, Natalia V.; Bahrami, Maryam; Ghaed-Sharaf, Tahereh; Ghatee, Mohammad Hadi; Seddon, Kenneth R.; Baldelli, Steven

    2018-05-01

    Sum frequency generation (SFG) spectroscopy is a nonlinear vibrational spectroscopic technique used in the study of interfaces, due to its unique ability to distinguish surface molecules that have preferential ordering compared to the isotropic bulk. Here, a series of alkyltrioctylphosphonium chloride ionic liquids, systematically varied by cation structure, were characterized at the air-liquid interface by SFG. The effect on surface structure resulting from molecular variation (i.e., addition of cyano- and methoxy-functional groups) of the cation alkyl chain was investigated. SFG spectra in the C—H stretching region (2750-3100 cm-1) for [P8 8 8 n][Cl], where n = 4, 5, 8, 10, 12, or 14, showed characteristic changes as the alkyl chain length was increased. Spectral profiles for n = 4, 5, 8, or 10 appeared similar; however, when the fourth alkyl chain was sufficiently long (as in the case of n = 12 or n = 14), abrupt changes occurred in the spectra. Molecular dynamics (MD) simulation of a slab of each ionic liquid (with n = 8, 10, or 12) confirmed gauche defects, with enhancement for the long alkyl chain and an abrupt increase of gauche occurrence from n = 8 to n = 10. A comparison of the tilt angle distribution from the simulation and the SFG analysis show a broad distribution of angles. Using experimental SFG spectra in conjunction with MD simulations, a comprehensive molecular picture at the surface of this unique class of liquids is presented.

  1. Sum-Frequency-Generation-Based Laser Sidebands for Tunable Femtosecond Raman Spectroscopy in the Ultraviolet

    Directory of Open Access Journals (Sweden)

    Liangdong Zhu

    2015-04-01

    Full Text Available Femtosecond stimulated Raman spectroscopy (FSRS is an emerging molecular structural dynamics technique for functional materials characterization typically in the visible to near-IR range. To expand its applications we have developed a versatile FSRS setup in the ultraviolet region. We use the combination of a narrowband, ~400 nm Raman pump from a home-built second harmonic bandwidth compressor and a tunable broadband probe pulse from sum-frequency-generation-based cascaded four-wave mixing (SFG-CFWM laser sidebands in a thin BBO crystal. The ground state Raman spectrum of a laser dye Quinolon 390 in methanol that strongly absorbs at ~355 nm is systematically studied as a standard sample to provide previously unavailable spectroscopic characterization in the vibrational domain. Both the Stokes and anti-Stokes Raman spectra can be collected by selecting different orders of SFG-CFWM sidebands as the probe pulse. The stimulated Raman gain with the 402 nm Raman pump is >21 times larger than that with the 550 nm Raman pump when measured at the 1317 cm−1 peak for the aromatic ring deformation and ring-H rocking mode of the dye molecule, demonstrating that pre-resonance enhancement is effectively achieved in the unique UV-FSRS setup. This added tunability in the versatile and compact optical setup enables FSRS to better capture transient conformational snapshots of photosensitive molecules that absorb in the UV range.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. 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...

  7. 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

  8. Lateral Vibration of Hydroelectric Generating Set with Different Supporting Condition of Thrust Pad

    Directory of Open Access Journals (Sweden)

    Xiaohui Si

    2011-01-01

    Full Text Available The variations of the supporting condition, which change the stiffness of tilting pad thrust bearing, may alter the dynamic behavior of the rotor system. The effects of supporting condition of thrust pad on the lateral vibration of a hydroelectric generating set are investigated in this paper. The action of a thrust bearing is described as moments acting on the thrust collar, and the tilting stiffness coefficients of thrust bearing are calculated. A model based on typical beam finite element method is established to calculate the dynamic response, and the effects of supporting conditions such as elastic oil tank support, different heights of the thrust pads with rigid support are discussed. The results reveal that the influence of thrust bearing is small when the elastic oil tanks work normally. When the supporting conditions turn to be rigid due to the oil leakage, the differences of thrust pad heights have evident influence on the load distribution of the thrust pads; while the effects on the tilting stiffness of the thrust bearing and the amplitude of the lateral shaft vibration is small when the maximum load on thrust pads is smaller than the allowable value.

  9. 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.

  10. 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.

  11. 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.

  12. Predictive analyses of flow-induced vibration and fretting wear in steam generator tubes

    International Nuclear Information System (INIS)

    Axisa, F.

    1989-01-01

    Maintaining the service life of PWR steam generators under highly reliable conditions requires a complex design to prevent various damaging processes, including those related to flow induced vibration. Predictive analyses have to rely on numerical tools to compute the vibratory response of multi-supported tubes in association with experimental data and semi-empirical relationships for quantifying flow-induced excitation mechanisms and tube damaging processes. In the presence of loose supports tube dynamics becomes highly nonlinear in nature. To deal with such problems CEA and FRAMATOME developed a computer program called GERBOISE. This paper provides a short description of an experimental program currently in progress at CEN Saclay to validate the numerical methods implemented in GERBOISE. According to the results obtained so far reasonable agreement is obtained between experiment and numerical simulation, especially as averaged quantities are concerned

  13. Influence of treatment by vibration in residual stress generated in the laser welding of HSLA and IF steels

    International Nuclear Information System (INIS)

    Chuvas, T.C.; Fonseca, M.P. Cindra; Castello, D.A.

    2010-01-01

    The stress relieving treatment by vibration is a new technology under development, which has many advantages over thermal methods. In this work was analyzed the surface residual stress generated in the laser welding of biphasic HSLA and IF steels, both used in the automotive industry. Residual stresses were measured by X-ray diffraction, by the sen 2 Ψ method. Residual stresses generated in the welding of the samples were tensile at all points measured. After welding, the samples were submitted to the mechanical vibration treatment. Some samples presented a significant reduction in the stress values. The welded joints were also characterized by optical microscopy. (author)

  14. 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.

  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. 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.

  17. 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...

  18. Numerical Research on Hydraulically Generated Vibration and Noise of a Centrifugal Pump Volute with Impeller Outlet Width Variation

    Directory of Open Access Journals (Sweden)

    Houlin Liu

    2014-01-01

    Full Text Available The impeller outlet width of centrifugal pumps is of significant importance for numbers of effects. In the paper, these effects including the performance, pressure pulsations, hydraulically generated vibration, and noise level are investigated. For the purpose, two approaches were used to predict the vibration and sound radiation of the volute under fluid excitation force. One approach is the combined CFD/FEM analysis for structure vibration, and then the structure response obtained from the FEM analysis is treated as the boundary condition for BEM analysis for sound radiation. The other is the combined CFD/FEM/BEM coupling method. Before the numerical methods were used, the simulation results were validated by the vibration acceleration of the monitoring points on the volute. The vibration and noise were analyzed and compared at three flow conditions. The analysis of the results shows that the influences of the sound pressure of centrifugal pumps on the structure appear insignificant. The relative outlet width b2* at nq(SI = 26.7 in this paper should be less than 0.06, based on an overall consideration of the pump characteristics, pressure pulsations, vibration and noise level.

  19. 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.

  20. 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.

  1. 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.

  2. 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...

  3. 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...

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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).

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. Influence of water depth on the sound generated by air-bubble vibration in the water musical instrument

    Science.gov (United States)

    Ohuchi, Yoshito; Nakazono, Yoichi

    2014-06-01

    We have developed a water musical instrument that generates sound by the falling of water drops within resonance tubes. The instrument can give people who hear it the healing effect inherent in the sound of water. The sound produced by falling water drops arises from air- bubble vibrations. To investigate the impact of water depth on the air-bubble vibrations, we conducted experiments at varying values of water pressure and nozzle shape. We found that air-bubble vibration frequency does not change at a water depth of 50 mm or greater. Between 35 and 40 mm, however, the frequency decreases. At water depths of 30 mm or below, the air-bubble vibration frequency increases. In our tests, we varied the nozzle diameter from 2 to 4 mm. In addition, we discovered that the time taken for air-bubble vibration to start after the water drops start falling is constant at water depths of 40 mm or greater, but slower at depths below 40 mm.

  16. Adding a dimension to the infrared spectra of interfaces using heterodyne detected 2D sum-frequency generation (HD 2D SFG) spectroscopy.

    Science.gov (United States)

    Xiong, Wei; Laaser, Jennifer E; Mehlenbacher, Randy D; Zanni, Martin T

    2011-12-27

    In the last ten years, two-dimensional infrared spectroscopy has become an important technique for studying molecular structures and dynamics. We report the implementation of heterodyne detected two-dimensional sum-frequency generation (HD 2D SFG) spectroscopy, which is the analog of 2D infrared (2D IR) spectroscopy, but is selective to noncentrosymmetric systems such as interfaces. We implement the technique using mid-IR pulse shaping, which enables rapid scanning, phase cycling, and automatic phasing. Absorptive spectra are obtained, that have the highest frequency resolution possible, from which we extract the rephasing and nonrephasing signals that are sometimes preferred. Using this technique, we measure the vibrational mode of CO adsorbed on a polycrystalline Pt surface. The 2D spectrum reveals a significant inhomogenous contribution to the spectral line shape, which is quantified by simulations. This observation indicates that the surface conformation and environment of CO molecules is more complicated than the simple "atop" configuration assumed in previous work. Our method can be straightforwardly incorporated into many existing SFG spectrometers. The technique enables one to quantify inhomogeneity, vibrational couplings, spectral diffusion, chemical exchange, and many other properties analogous to 2D IR spectroscopy, but specifically for interfaces.

  17. 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.

  18. 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.

  19. Vibration Testing of the NASA Constellation X Spectroscopy X-Ray Telescope Reflectors

    National Research Council Canada - National Science Library

    Carlson, Andrew

    2004-01-01

    .... The data will help the Mechanical Systems Engineering Team of the SXT portion of the Con-X program at NASA-GSFC determine whether the reflectors will survive the loads generated in a launch environment...

  20. Operational Safety Assessment of Turbo Generators with Wavelet Rényi Entropy from Sensor-Dependent Vibration Signals

    Directory of Open Access Journals (Sweden)

    Xiaoli Zhang

    2015-04-01

    Full Text Available With the rapid development of sensor technology, various professional sensors are installed on modern machinery to monitor operational processes and assure operational safety, which play an important role in industry and society. In this work a new operational safety assessment approach with wavelet Rényi entropy utilizing sensor-dependent vibration signals is proposed. On the basis of a professional sensor and the corresponding system, sensor-dependent vibration signals are acquired and analyzed by a second generation wavelet package, which reflects time-varying operational characteristic of individual machinery. Derived from the sensor-dependent signals’ wavelet energy distribution over the observed signal frequency range, wavelet Rényi entropy is defined to compute the operational uncertainty of a turbo generator, which is then associated with its operational safety degree. The proposed method is applied in a 50 MW turbo generator, whereupon it is proved to be reasonable and effective for operation and maintenance.

  1. Design specifications to ensure flow-induced vibration and fretting-wear performance in CANDU steam generators and heat exchangers

    International Nuclear Information System (INIS)

    Janzen, V.P.; Han, Y.; Pettigrew, M.J.

    2009-01-01

    Preventing flow-induced vibration and fretting-wear problems in steam generators and heat exchangers requires design specifications that bring together specific guidelines, analysis methods, requirements and appropriate performance criteria. This paper outlines the steps required to generate and support such design specifications for CANDU nuclear steam generators and heat exchangers, and relates them to typical steam-generator design features and computer modeling capabilities. It also describes current issues that are driving changes to flow-induced vibration and fretting-wear specifications that can be applied to the design process for component refurbishment, replacement or new designs. These issues include recent experimental or field evidence for new excitation mechanisms, e.g., the possibility of in-plane fluidelastic instability of U-tubes, the demand for longer reactor and component lifetimes, the need for better predictions of dynamic properties and vibration response, e.g., two-phase random-turbulence excitation, and requirements to consider system 'excursions' or abnormal scenarios, e.g., a main steam line break in the case of steam generators. The paper describes steps being taken to resolve these issues. (author)

  2. WEAVE: the next generation wide-field spectroscopy facility for the William Herschel Telescope : The next generation wide-field spectroscopy facility for the William Herschel Telescope

    NARCIS (Netherlands)

    Dalton, Gavin; Trager, Scott C.; Abrams, Don Carlos; Carter, David; Bonifacio, Piercarlo; Aguerri, J. Alfonso L.; MacIntosh, Mike; Evans, Chris; Lewis, Ian; Navarro, Ramon; Agocs, Tibor; Dee, Kevin; Rousset, Sophie; Tosh, Ian; Middleton, Kevin; Pragt, Johannes; Terrett, David; Brock, Matthew; Benn, Chris; Verheijen, Marc; Cano Infantes, Diego; Bevil, Craige; Steele, Iain; Mottram, Chris; Bates, Stuart; Gribbin, Francis J.; Rey, Jürg; Rodriguez, Luis Fernando; Delgado, Jose Miguel; Guinouard, Isabelle; Walton, Nic; Irwin, Michael J.; Jagourel, Pascal; Stuik, Remko; Gerlofsma, Gerrit; Roelfsma, Ronald; Skillen, Ian; Ridings, Andy; Balcells, Marc; Daban, Jean-Baptiste; Gouvret, Carole; Venema, Lars; Girard, Paul

    We present the preliminary design of the WEAVE next generation spectroscopy facility for the William Herschel Telescope (WHT), principally targeting optical ground-based follow up of upcoming ground-based (LOFAR) and spacebased (Gaia) surveys. WEAVE is a multi-object and multi-IFU facility utilizing

  3. 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)

  4. 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

  5. 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.

  6. 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.

  7. 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...

  8. Vibrational Dynamics of Interfacial Water by Free Induction Decay Sum Frequency Generation (FID-SFG) at the Al2O3(1120)/H2O Interface.

    Science.gov (United States)

    Boulesbaa, Abdelaziz; Borguet, Eric

    2014-02-06

    The dephasing dynamics of a vibrational coherence may reveal the interactions of chemical functional groups with their environment. To investigate this process at a surface, we employ free induction decay sum frequency generation (FID-SFG) to measure the time that it takes for free OH stretch oscillators at the charged (pH ≈ 13, KOH) interface of alumina/water (Al2O3/H2O) to lose their collective coherence. By employing noncollinear optical parametric amplification (NOPA) technology and nonlinear vibrational spectroscopy, we showed that the single free OH peak actually corresponds to two distinct oscillators oriented opposite to each other and measured the total dephasing time, T2, of the free OH stretch modes at the Al2O3/H2O interface with a sub-40 fs temporal resolution. Our results suggested that the free OH oscillators associated with interfacial water dephase on the time scale of 89.4 ± 6.9 fs, whereas the homogeneous dephasing of interfacial alumina hydroxyls is an order of magnitude slower.

  9. Development of Design Criteria for Fluid Induced Structural Vibrations in Steam Generators and Heat Exchangers

    International Nuclear Information System (INIS)

    Uvan Catton; Dhir, Vijay K.; Deepanjan Mitra; Omar Alquaddoomi; Pierangelo Adinolfi

    2004-01-01

    Flow-induced vibration in heat exchangers has been a major cause of concern in the nuclear industry for several decades. Many incidents of failure of heat exchangers due to apparent flow-induced vibration have been reported through the USNRC incident reporting system. Almost all heat exchangers have to deal with this problem during their operation. The phenomenon has been studied since the 1970s and the database of experimental studies on flow-induced vibration is constantly updated with new findings and improved design criteria for heat exchangers

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 2D heterodyne-detected sum frequency generation study on the ultrafast vibrational dynamics of H{sub 2}O and HOD water at charged interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Ken-ichi; Singh, Prashant C. [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nihonyanagi, Satoshi; Tahara, Tahei, E-mail: tahei@riken.jp [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Yamaguchi, Shoichi [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Department of Applied Chemistry, Saitama University, 255 Shimo-Okubo, Saitama 338-8570 (Japan)

    2015-06-07

    Two-dimensional heterodyne-detected vibrational sum-frequency generation (2D HD-VSFG) spectroscopy is applied to study the ultrafast vibrational dynamics of water at positively charged aqueous interfaces, and 2D HD-VSFG spectra of cetyltrimethylammonium bromide (CTAB)/water interfaces in the whole hydrogen-bonded OH stretch region (3000 cm{sup −1} ≤ ω{sub pump} ≤ 3600 cm{sup −1}) are measured. 2D HD-VSFG spectrum of the CTAB/isotopically diluted water (HOD-D{sub 2}O) interface exhibits a diagonally elongated bleaching lobe immediately after excitation, which becomes round with a time constant of ∼0.3 ps due to spectral diffusion. In contrast, 2D HD-VSFG spectrum of the CTAB/H{sub 2}O interface at 0.0 ps clearly shows two diagonal peaks and their cross peaks in the bleaching region, corresponding to the double peaks observed at 3230 cm{sup −1} and 3420 cm{sup −1} in the steady-state HD-VSFG spectrum. Horizontal slices of the 2D spectrum show that the relative intensity of the two peaks of the bleaching at the CTAB/H{sub 2}O interface gradually change with the change of the pump frequency. We simulate the pump-frequency dependence of the bleaching feature using a model that takes account of the Fermi resonance and inhomogeneity of the OH stretch vibration, and the simulated spectra reproduce the essential features of the 2D HD-VSFG spectra of the CTAB/H{sub 2}O interface. The present study demonstrates that heterodyne detection of the time-resolved VSFG is critically important for studying the ultrafast dynamics of water interfaces and for unveiling the underlying mechanism.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. Study on antilock brake system with elastic membrane vibration generated by controlled solenoid excitation

    International Nuclear Information System (INIS)

    Wibowo,; Zakaria,; Lambang, Lullus; Triyono,; Muhayat, Nurul

    2016-01-01

    The most effective chassis control system for improving vehicle safety during severe braking is anti-lock braking system (ABS). Antilock effect can be gained by vibrate the pad brake at 7 to 20 cycle per second. The aim of this study is to design a new method of antilock braking system with membrane elastic vibrated by solenoid. The influence of the pressure fluctuations of brake fluid is investigated. Vibration data is collected using a small portable accelerometer-slam stick. The experiment results that the vibration of brake pad caused by controlled solenoid excitation at 10 Hz is obtained by our new method. The result of measurements can be altered by varying brake fluid pressure.

  8. Study on antilock brake system with elastic membrane vibration generated by controlled solenoid excitation

    Energy Technology Data Exchange (ETDEWEB)

    Wibowo,, E-mail: wibowo-uns@yahoo.com; Zakaria,, E-mail: zakaaria27@gmail.com; Lambang, Lullus, E-mail: lulus-l@yahoo.com; Triyono,, E-mail: tyon-bila@yahoo.co.id; Muhayat, Nurul, E-mail: nurulmuhayat@ymail.com [Mechanical Engineering Department, Sebelas Maret University, Surakarta 57128 (Indonesia)

    2016-03-29

    The most effective chassis control system for improving vehicle safety during severe braking is anti-lock braking system (ABS). Antilock effect can be gained by vibrate the pad brake at 7 to 20 cycle per second. The aim of this study is to design a new method of antilock braking system with membrane elastic vibrated by solenoid. The influence of the pressure fluctuations of brake fluid is investigated. Vibration data is collected using a small portable accelerometer-slam stick. The experiment results that the vibration of brake pad caused by controlled solenoid excitation at 10 Hz is obtained by our new method. The result of measurements can be altered by varying brake fluid pressure.

  9. Performance of Different Sensors for Monitoring of the Vibration Generated during Thermosonic Non-destructive Testing

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Bu Byoung [Korea Railroad Research Institute, Uiwang (Korea, Republic of)

    2011-04-15

    Vibration monitoring is required for reliable thermosonic testing to decide whether sufficient vibration is achieved in each test for the detection of cracks. From a practical point of view, a cheaper and convenient monitoring method is better for the application to real tests. Therefore, the performance of different sensors for vibration monitoring was investigated and compared in this study to find a convenient and acceptable measurement method for thermosonics. Velocity measured by a laser vibrometer and strain provide an equivalent HI when measured at the same position. The microphone can provide a cheaper vibration monitoring device than the laser and the heating index calculated by a microphone signal shows similar characteristics to that calculated from velocity measured by the laser vibrometer. The microphone frequency response shows that it underestimates high frequency components but it is applicable to practical tests because it gives a conservative value of HI

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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)

  15. Application of flow-induced vibration predictive techniques to operating steam generators

    International Nuclear Information System (INIS)

    Sauve, R.G.; Tabatabai, M.; Morandin, G.; Kozluk, M.J.

    1998-01-01

    Analytical techniques for flow-induced vibration (FIV), such as those incorporated in available design tools, are routinely applied to process equipment at the initial design stage. Unfortunately, this does not always apply to the situation when problems, related to FIV, develop in crucial operating equipment, since design uses conservative methods, whereas in-service applications require more realistic assessments. Usually these problems appear in the form of severe through wall fret flaws or fatigue cracks that compromise the integrity of the tubes and possibly the complete unit. It is here where a somewhat different approach must be taken in the evaluation of tube response to FIV. Tube damage from fretting wear or fatigue crack growth must be estimated from actual in situ operating conditions. In this paper, an overview of the predictive methods used in the development and/or qualification of remedial measures for problems that occur in operating process equipment along with applications are described. The steps in the evaluation procedure, from the prediction of flow regimes, the development of the nonlinear computer models and associated fluid forcing functions through to the estimates of tube damage in operating heat exchangers and steam generators are presented. A probabilistic (i.e. Monte Carlo simulation) FIV approach that readily accommodates uncertainties associated with damage predictions is summarized. The efficacy of this approach comes from the fact that probabilistic methods facilitate the incorporation of field data, and that a large number of tubes and possible variations in geometry, process and support conditions, usually present in such equipment, can be addressed effectively. (author)

  16. Experimental modeling of flow-induced vibration of multi-span U-tubes in a CANDU steam generator

    International Nuclear Information System (INIS)

    Mohany, A.; Feenstra, P.; Janzen, V.P.; Richard, R.

    2009-01-01

    Flow-induced vibration of the tubes in a nuclear steam generator is a concern for designers who are trying to increase the life span of these units. The dominant excitation mechanisms are fluidelastic instability and random turbulence excitation. The outermost U-bend region of the tubes is of greatest concern because the flow is almost perpendicular to the tube axis and the unsupported span is relatively long. The support system in this region must be well designed in order to minimize fretting wear of the tubes at the support locations. Much of the previous testing was conducted on straight single-span or cantilevered tubes in cross-flow. However, the dynamic response of steam generator multi-span U-tubes with clearance supports is expected to be different. Accurate modeling of the tube dynamics is important to properly simulate the dynamic interaction of the tube and supports. This paper describes a test program that was developed to measure the dynamic response of a bundle of steam generator U-tubes with Anti-Vibration Bar (AVB) supports, subjected to Freon two-phase cross-flow. The tube bundle has similar geometrical conditions to those expected for future CANDU steam generators. Future steam generators will be larger than previous CANDU steam generators, nearly twice the heat transfer area, with significant changes in process conditions in the U-bend region, such as increased steam quality and a broader range of flow velocities. This test program was initiated at AECL to demonstrate that the tube support design for future CANDU steam generators will meet the stringent requirements associated with a 60 year design life. The main objective of the tests is to address the issue of in-plane and out-of-plane fluidelastic instability and random turbulent excitation of a U-tube bundle with Anti-Vibration Bar (AVB) supports. Details of the test rig, measurement techniques and preliminary instrumentation results are described in the paper. (author)

  17. Analysis of flow-induced vibration of heat exchanger and steam generator tube bundles using the AECL computer code PIPEAU-2

    International Nuclear Information System (INIS)

    Gorman, D.J.

    1983-12-01

    PIPEAU-2 is a computer code developed at the Chalk River Nuclear Laboratories for the flow-induced vibration analysis of heat exchanger and steam generator tube bundles. It can perform this analysis for straight and 'U' tubes. All the theoretical work underlying the code is analytical rather than numerical in nature. Highly accurate evaluation of the free vibration frequencies and mode shapes is therefore obtained. Using the latest experimentally determined parameters available, the free vibration analysis is followed by a forced vibration analysis. Tube response due to fluid turbulence and vortex shedding is determined, as well as critical fluid velocity associated with fluid-elastic instability

  18. High-temperature laser induced spectroscopy in nuclear steam generators

    International Nuclear Information System (INIS)

    Allmon, W.E.; Berthold, J.W.

    1990-01-01

    This patent describes an apparatus for conducting optical spectroscopy in a hostile environment. It comprises: a source of high intensity light; an optical fiber connected to the source of high intensity light for transmitting light therefrom. The optical fiber having an end for discharging light onto a material to be spectroscopically analyzed; a sheath defining a space around at least a part of the optical fiber carrying the end of the optical fiber for shielding the optical fiber from the hostile environment; a window in the sheath for closing the space and for passing light transmitted through the end of the optical fiber out of the sheath; light detector means for detecting and spectroscopically analyzing emitted light from the material; an optical fiber means for transmitting the emitted light from the material to the light detector means; a standardization module for containing a sample having a known composition and being exposed to known temperature and pressure conditions; an additional optical fiber connected to the module for transmitting light to the sample in the module; multiplexer means; and additional optical fiber means for returning light from the module to the detector through the multiplexer means

  19. Corrosion of steam generator pipelines analysed using Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Slugen, V.; Lipka, J.; Toth, I.; Hascik, J.; Hinca, R.; Lehota, M.

    2003-01-01

    The variability of the properties and the composition of the corrosion products of the stainless CrNi and mild steels in dependence on the conditions (temperature, acidity, etc.) is of such range that, in practice, it is impossible to determine the properties of the corrosion products for an actual case from the theoretical data only. Since the decontamination processes for the materials of the water-cooled reactor (VVER-440) secondary circuits are in the progress of development, it is necessary to draw the needed information by the measurement and analysis of the real specimens. The corrosion layers was separated by scraping the rust off the surface and the powder samples were studied by transmission Moessbauer spectroscopy. It should be noted that the gamma spectroscopic measurements give no evidence of the presence of low-energy gamma radiation emitted from the samples. The scraped specimen powder was homogenised (using a 50 μm sieve) and fixed into a special holder. The 57 Co in Rh matrix was used as the radioactive Moessbauer source. Measured spectra were fitted using program NORMOS SITE. According to the results obtained from Moessbauer spectra, it is possible to establish that the main component of secondary circuit's corrosion products is magnetite Fe 3 O 4 . Next components are hematite α-Fe 2 O 3 and hydroxide akagenite β-FeOOH, which is characterised by significant paramagnetic doublet in the middle of spectra. The sextets corresponding to base materials (martensite and austenite steels) were identified in all measured spectra. (author)

  20. 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.

  1. ENIDINE: Vibration and seismic isolation technologies for power generation station applications

    International Nuclear Information System (INIS)

    Zemanek, T.A.

    1994-01-01

    ENIDINE Inc. is a world leader in the design and manufacture of shock and vibration mounts. Founded in 1966, the company has two manufacturing facilities, employs over 300 people and supports a worldwide network of distributors and representatives. ENIDINE Inc. is part of the ENIDINE Corporate Group which owns a number of companies that design and manufacture Hydraulic/Pneumatic cylinders, Electromechanical devices, Hydraulic Control Valves and a number of Industrial Distribution companies throughout Europe. In total, the ENIDINE Corporate Group has over 900 employees with annual sales of over $100 million. ENIDINE shock and vibration mounts are used to isolate the vibration of missiles from their guidance systems, pumps from hospital operating equipment and off shore oil rigs, from the shock energy of waves in the North Sea. ENIDINE products can be found on all Boeing and McDonnell Douglas aircraft, as well as many electronic and weapons systems on board Navy ships

  2. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    Energy Technology Data Exchange (ETDEWEB)

    Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C6H11) and π-allyl C6H9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C6H9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C6H9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E2u mode of free benzene, which leads to catalysis. Linear C6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

  3. Interpreting intensities in vibrational sum frequency generation (SFG) spectroscopy: CO adsorption on Pd surfaces

    Science.gov (United States)

    Morkel, M.; Unterhalt, H.; Klüner, T.; Rupprechter, G.; Freund, H.-J.

    2005-07-01

    The lineshape and intensity of SFG signals of CO adsorbed on supported Pd nanoparticles and Pd(1 1 1) are analyzed. For CO/Pd(1 1 1) nearly symmetric lorentzian lineshapes were observed. Applying two different visible wavelengths for excitation, asymmetric lineshapes observed for the CO/Pd/Al 2O 3/NiAl(1 1 0) system are explained by a lower resonant and a higher non-resonant SFG signal and a change in the phase between resonant and non-resonant signals, most likely originating from an interband transition in the NiAl substrate. The relative intensity of different CO species (hollow, bridge, on-top) was modeled by DFT calculations of IR transition moments and Raman activities. While the (experimental) sensitivity of SFG towards different CO species strongly varies, the calculated IR and Raman activities are rather similar. The inability to exactly reproduce experimental SFG intensities suggests a strong coverage dependence of Raman activities or that non-linear effects occur that can currently not be properly accounted for.

  4. Experimental studies on flow-induced vibration to support steam generator design

    International Nuclear Information System (INIS)

    Pettigrew, M.J.; Gorman, D.J.

    1977-06-01

    Vibration experiments were done on small tube bundles of triangular and square lattice configurations in both liquid and two-phase (air-water) cross-flow. The effects of flow velocity, simulated steam quality, lattice orientation, tube location and tube frequency were explored. Tube response to random flow turbulence excitation and fluidelastic instability were observed in both liquid and two-phase cross-flow. Fluidelastic instability criteria and random forcing function characterizations are derived from this work. This information may be used in the vibration analysis of shell-and-tube heat exchanger components. (author)

  5. 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.

  6. Vibration reduction and power generation with piezoceramic sheets mounted to a flexible shaft

    NARCIS (Netherlands)

    Sloetjes, P.J.; de Boer, Andries

    2008-01-01

    A flexible shaft with surface-mounted piezoceramic sheets and strain sensors is considered which suffers from resonance and self-excited vibration. Frequency domain models, time domain simulations, and control experiments are used to analyze active modal damping and active modal balancing methods.

  7. Mobile charge generation dynamics in P3HT: PCBM observed by time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Cooke, D. G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2012-01-01

    Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale.......Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale....

  8. Flow-induced vibration and fretting-wear specifications to ensure steam-generator and heat exchanger lifetime performance

    International Nuclear Information System (INIS)

    Janzen, V.P.; Han, Y.; Pettigrew, M.J.

    2008-01-01

    The current interest in refurbishment, life extension and new-build activity has meant a renewed emphasis on technical specifications that will ensure improved reliability and longer life. Preventing vibration and fretting-wear problems in steam generators and heat exchangers requires design specifications that bring together specific guidelines, analysis methods, requirements and appropriate performance criteria. The specifications must be firmly based on experimental data and field inspections. In addition, the specifications must be supported by theoretical analyses and fundamental scaling correlations, to cover conditions and geometries over the wide range applicable to existing components and probable future designs. The specifications are expected to evolve to meet changing industry requirements. This paper outlines the steps required to generate and support design specifications, and relates them to typical steam-generator design features and computer modeling capabilities. It also describes current issues that are driving changes to flow-induced vibration and fretting-wear specifications that can be applied to the design process for component refurbishment, replacement or new designs. These issues include recent experimental or field evidence for new excitation mechanisms, e.g., the possibility of in-plane fluidelastic instability of U-tubes, the demand for longer reactor and component lifetimes, the need for better predictions of dynamic properties and vibration response, e.g., two-phase random-turbulence excitation, and requirements to consider system 'excursions' or abnormal scenarios, e.g., a main steam line break in the case of steam generators. The paper describes steps being taken to resolve these issues. (author)

  9. 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

  10. 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....

  11. Some causes of vibrations recorded by in-service diagnostic systems in steam generators of units 1 and 2 of Dukovany nuclear power plant

    International Nuclear Information System (INIS)

    Sadilek, J.; Matal, O.

    1989-01-01

    A brief description is presented of the design of the steam generators of the first and second units of the Dukovany nuclear power plant. Attention is also given to the feed water systems and the diagnostic systems. The causes are analyzed of the irregularly occurring vibrations in the steam generators in service. It is demonstrated that the source of the vibrations transmitted to the steam generators are the valves in the feeding tract. The vibrations are induced by dynamic forces from the feed water. Reducing the water pressure at the delivery of the electric feed pumps by reducing the size of the rotor, etc., does not remove all vibrations. It is therefore recommended that valves be ins+alled with better regulating characteristics. (Z.M.). 6 figs., 1 tab., 3 refs

  12. 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.

  13. 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.

  14. 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...

  15. Impulsive IR-multiphoton dissociation of acrolein: observation of non-statistical product vibrational excitation in CO ( v=1-12) by time resolved IR fluorescence spectroscopy

    Science.gov (United States)

    Chowdhury, P. K.

    2000-10-01

    On IR-multiphoton excitation, vibrationally highly excited acrolein molecules undergo concerted dissociation generating CO and ethylene. The vibrationally excited products, CO and ethylene, are detected immediately following the CO 2 laser pulse by observing IR fluorescence at 4.7 and 3.2 μm, respectively. The nascent CO is formed with significant vibrational excitation, with a Boltzmann population distribution for v=1-12 levels corresponding to T v=12 950±50 K. The average vibrational energy in the product CO is found to be 26 kcal mol -1, in contrast to its statistical share of 5 kcal mol -1, available from the product energy distribution. The nascent vibrationally excited ethylene either dissociates by absorbing further infrared laser photons from the tail of the CO 2 laser pulse or relaxes by collisional deactivation. Ethylene IR-fluorescence excitation spectrum showed a structure in the quasi-continuum, with a facile resonance at 10.53 μm corresponding to the 10P(14) CO 2 laser line, which explains the higher acetylene yield observed at a higher pressure. A hydrogen atom transfer mechanism followed by C-C impulsive break in the acrolein transition state may be responsible for such non-statistical product energy distribution.

  16. Vibrations Generated by Several Nickel-titanium Endodontic File Systems during Canal Shaping in an Ex Vivo Model.

    Science.gov (United States)

    Choi, Dong-Min; Kim, Jin-Woo; Park, Se-Hee; Cho, Kyung-Mo; Kwak, Sang Won; Kim, Hyeon-Cheol

    2017-07-01

    This study aimed to compare the vibration generated by several nickel-titanium (NiTi) file systems and transmitted to teeth under 2 different motions (continuous rotation motion and reciprocating motion). Sixty J-shaped resin blocks (Endo Training Bloc-J; Dentsply Maillefer, Ballaigues, Switzerland) were trimmed to a root-shaped form and divided into 2 groups according to the types of electric motors: WaveOne motor (WOM, Dentsply Maillefer) and X-Smart Plus motor (XSM, Dentsply Maillefer). Each group was further subdivided into 3 subgroups (n = 10 each) according to the designated file systems: ProTaper Next (PTN, Dentsply Maillefer), ProTaper Universal (PTU, Dentsply Maillefer), and WaveOne (WOP, Dentsply Maillefer) systems. Vibration was measured during the pecking motion using an accelerometer attached to a predetermined consistent position. The average vibration values were subjected to 2-way analysis of variance as well as the t test and Duncan test for post hoc comparison at the 95% confidence interval. Both motor types and instrument types produced significantly different ranges of average vibrations. Regardless of the instrument types, the WOM group generated greater vibration than the XSM group (P file system may generate greater vibration than the continuous rotation NiTi file systems. The motor type also has a significant effect to amplify the vibrations. Copyright © 2017 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  17. Vibrations as a contributor to the cracking of PGV-1000 steam generator cold collector

    International Nuclear Information System (INIS)

    Verezemskij, V.G.

    1997-01-01

    The results of multiple investigations of cold collector ruptures at NPPs with WWER-1000 reactor as a complex and multi-parameter process are generalized. It is shown that the temperature of cold collector operation (280-290 deg C) at which environment corrosion effects are maximum has an important role for revealing the factors causing the damage. When the reactor plant operates under stationary and transient conditions the primary coolant circuit equipment, main circulation pipelines and main steam lines become involved into vibrations with different intensities as a result of pressure pulsations at reverse and multiple frequencies of the main circulation pumps connected with formation of standing pressure waves in the primary circuit and steam lines. The analysis made gives an opportunity to conclude that dynamic loads (vibrations) play the leading part in reaching the limits of cold collector metal cyclic strength and its cracking. It means that the measures for cold collector service life increasing should be directed on vibration amplitude lowering and cyclic stress decreasing

  18. 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.

  19. 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)

  20. 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

  1. 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.

  2. 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.

  3. Model Catalysis of Ammonia Synthesis ad Iron-Water Interfaces - ASum Frequency Generation Vibrational Spectroscopic Study of Solid-GasInterfaces and Anion Photoelectron Spectroscopic Study of Selected Anionclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, Michael James [Univ. of California, Berkeley, CA (United States)

    2005-01-01

    The ammonia synthesis reaction has been studied using single crystal model catalysis combined with sum frequency generation (SFG) vibrational spectroscopy. 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 or equilibrium concentrations of reactants and products on Fe(111) surfaces. Special attention was paid to understand how potassium promotion of the iron catalyst affects the intermediates of ammonia synthesis. An Fe(111) surface promoted with 0.2 monolayers of potassium red shifts the vibrational frequencies of the reactive surface intermediates, NH and NH2, providing evidence for weakened the nitrogen-hydrogen bonds relative to clean Fe(111). Spectral features of these surface intermediates persisted to higher temperatures for promoted iron surfaces than for clean Fe(111) surfaces implying that nitrogen-iron bonds are stronger for the promoted surface. The ratio of the NH to NH2 signal changed for promoted surfaces in the presence of equilibrium concentrations of reactants and products. The order of adding oxygen and potassium to promoted surfaces does not alter the spectra indicating that ammonia induces surface reconstruction of the catalyst to produce the same surface morphology. When oxygen is co-adsorbed with nitrogen, hydrogen, ammonia or potassium on Fe(111), a relative phase shift of the spectra occurs as compared to the presence of adsorbates on clean iron surfaces. Water adsorption on iron was also probed using SFG vibrational spectroscopy. For both H2O and D2O, the only spectral feature was in the range of

  4. Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Humbert, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France) and Laboratoire de Spectroscopie Moleculaire de Surface, University of Namur, 61 Rue de Bruxelles, B-5000 Namur (Belgium)]. E-mail: christophe.humbert@fundp.ac.be; Busson, B. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Abid, J.-P. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Six, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Girault, H.H. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Tadjeddine, A. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France)

    2005-05-20

    We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm{sup -1} spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment.

  5. Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

    International Nuclear Information System (INIS)

    Humbert, C.; Busson, B.; Abid, J.-P.; Six, C.; Girault, H.H.; Tadjeddine, A.

    2005-01-01

    We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm -1 spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment

  6. Low frequency noise and air vibration generated by a simple cycle gas turbine installation

    Energy Technology Data Exchange (ETDEWEB)

    Giesbrecht, C.; Hertil, S. [ATCO Noise Management, Calgary, AB (Canada)

    2005-07-01

    Low-frequency noise refers to infrasound whose frequency is lower than the minimum human audible frequency of about 20 Hz. Recently, there have been serious complaints on noise pollution in the frequency range of 1-100 Hz. This presentation outlined ASHRAE noise criteria regions and discussed human perceptions to vibration. It also presented methods that ATCO used for measuring noise at a simple gas turbine installation, inside the site at the administration buildings, at the paths of vibration and noise propagation, and at noise sensitive receptors. A 70 dBC at the closes noise-sensitive receptor was used as a noise limit to minimize annoyance. In addition, 96 dBC was measured at 400 feet. It was noted that reducing the C-weighted sound level depends on reducing the stack noise emissions in the 16 and 31.5 band levels. ATCO evaluated silencer designs and recommended reactive silencers to achieve a 10 dB reduction in noise emitted by the 3 exhaust stacks. 6 figs.

  7. Experimental evidence for an optical interference model for vibrational sum frequency generation on multilayer organic thin film systems. I. Electric dipole approximation

    International Nuclear Information System (INIS)

    O’Brien, Daniel B.; Massari, Aaron M.

    2015-01-01

    In the field of vibrational sum frequency generation spectroscopy (VSFG) applied to organic thin film systems, a significant challenge to data analysis is in the accurate description of optical interference effects. Herein, we provide experimental evidence that a model recently developed in our lab provides an accurate description of this phenomenon. We studied the organic small molecule N,N′-dioctyl-3,4,9,10-perylenedicarboximide vapor deposited as a thickness gradient on silicon wafer substrates with two oxide thicknesses and two surface preps. VSFG data were obtained using the ssp and the sps polarization combinations in the imide carbonyl stretching region as a function of organic thickness. In this first of two reports, the data are modeled and interpreted within the ubiquitous electric dipole approximation for VSFG. The intrinsic sample responses are parameterized during the fitting routines while optical interference effects are simply calculated from the model using known refractive indices, thin film thicknesses, and beam angles. The results indicate that the thin film model provides a good description of optical interferences, indicating that interfacial terms are significant. Inconsistencies between the fitting results within the bounds of the electric dipole response motivate deliberation for additional effects to be considered in the second report

  8. Experimental evidence for an optical interference model for vibrational sum frequency generation on multilayer organic thin film systems. I. Electric dipole approximation.

    Science.gov (United States)

    O'Brien, Daniel B; Massari, Aaron M

    2015-01-14

    In the field of vibrational sum frequency generation spectroscopy (VSFG) applied to organic thin film systems, a significant challenge to data analysis is in the accurate description of optical interference effects. Herein, we provide experimental evidence that a model recently developed in our lab provides an accurate description of this phenomenon. We studied the organic small molecule N,N'-dioctyl-3,4,9,10-perylenedicarboximide vapor deposited as a thickness gradient on silicon wafer substrates with two oxide thicknesses and two surface preps. VSFG data were obtained using the ssp and the sps polarization combinations in the imide carbonyl stretching region as a function of organic thickness. In this first of two reports, the data are modeled and interpreted within the ubiquitous electric dipole approximation for VSFG. The intrinsic sample responses are parameterized during the fitting routines while optical interference effects are simply calculated from the model using known refractive indices, thin film thicknesses, and beam angles. The results indicate that the thin film model provides a good description of optical interferences, indicating that interfacial terms are significant. Inconsistencies between the fitting results within the bounds of the electric dipole response motivate deliberation for additional effects to be considered in the second report.

  9. Experimental evidence for an optical interference model for vibrational sum frequency generation on multilayer organic thin film systems. I. Electric dipole approximation

    Energy Technology Data Exchange (ETDEWEB)

    O’Brien, Daniel B.; Massari, Aaron M., E-mail: massari@umn.edu [Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455 (United States)

    2015-01-14

    In the field of vibrational sum frequency generation spectroscopy (VSFG) applied to organic thin film systems, a significant challenge to data analysis is in the accurate description of optical interference effects. Herein, we provide experimental evidence that a model recently developed in our lab provides an accurate description of this phenomenon. We studied the organic small molecule N,N′-dioctyl-3,4,9,10-perylenedicarboximide vapor deposited as a thickness gradient on silicon wafer substrates with two oxide thicknesses and two surface preps. VSFG data were obtained using the ssp and the sps polarization combinations in the imide carbonyl stretching region as a function of organic thickness. In this first of two reports, the data are modeled and interpreted within the ubiquitous electric dipole approximation for VSFG. The intrinsic sample responses are parameterized during the fitting routines while optical interference effects are simply calculated from the model using known refractive indices, thin film thicknesses, and beam angles. The results indicate that the thin film model provides a good description of optical interferences, indicating that interfacial terms are significant. Inconsistencies between the fitting results within the bounds of the electric dipole response motivate deliberation for additional effects to be considered in the second report.

  10. 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.

  11. 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

  12. Use of a magnetic force exciter to vibrate a piezocomposite generating element in a small-scale windmill

    International Nuclear Information System (INIS)

    Luong, Hung Truyen; Goo, Nam Seo

    2012-01-01

    A piezocomposite generating element (PCGE) can be used to convert ambient vibrations into electrical energy that can be stored and used to power other devices. This paper introduces a design of a magnetic force exciter for a small-scale windmill that vibrates a PCGE to convert wind energy into electrical energy. A small-scale windmill was designed to be sensitive to low-speed wind in urban regions for the purpose of collecting wind energy. The magnetic force exciter consists of exciting magnets attached to the device’s input rotor and a secondary magnet fixed at the tip of the PCGE. The PCGE is fixed to a clamp that can be adjusted to slide on the windmill’s frame in order to change the gap between exciting and secondary magnets. Under an applied wind force, the input rotor rotates to create a magnetic force interaction that excites the PCGE. The deformation of the PCGE enables it to generate electric power. Experiments were performed with different numbers of exciting magnets and different gaps between the exciting and secondary magnets to determine the optimal configuration for generating the peak voltage and harvesting the maximum wind energy for the same range of wind speeds. In a battery-charging test, the charging time for a 40 mA h battery was approximately 3 h for natural wind in an urban region. The experimental results show that the prototype can harvest energy in urban regions with low wind speeds and convert the wasted wind energy into electricity for city use. (paper)

  13. High-resolution broadband terahertz spectroscopy via electronic heterodyne detection of photonically generated terahertz frequency comb.

    Science.gov (United States)

    Pavelyev, D G; Skryl, A S; Bakunov, M I

    2014-10-01

    We report an alternative approach to the terahertz frequency-comb spectroscopy (TFCS) based on nonlinear mixing of a photonically generated terahertz pulse train with a continuous wave signal from an electronic synthesizer. A superlattice is used as a nonlinear mixer. Unlike the standard TFCS technique, this approach does not require a complex double-laser system but retains the advantages of TFCS-high spectral resolution and wide bandwidth.

  14. Generation of interior cavity noise due to window vibration excited by turbulent flows past a generic side-view mirror

    Science.gov (United States)

    Yao, Hua-Dong; Davidson, Lars

    2018-03-01

    We investigate the interior noise caused by turbulent flows past a generic side-view mirror. A rectangular glass window is placed downstream of the mirror. The window vibration is excited by the surface pressure fluctuations and emits the interior noise in a cuboid cavity. The turbulent flows are simulated using a compressible large eddy simulation method. The window vibration and interior noise are predicted with a finite element method. The wavenumber-frequency spectra of the surface pressure fluctuations are analyzed. The spectra are identified with some new features that cannot be explained by the Chase model for turbulent boundary layers. The spectra contain a minor hydrodynamic domain in addition to the hydrodynamic domain caused by the main convection of the turbulent boundary layer. The minor domain results from the local convection of the recirculating flow. These domains are formed in bent elliptic shapes. The spanwise expansion of the wake is found causing the bending. Based on the wavenumber-frequency relationships in the spectra, the surface pressure fluctuations are decomposed into hydrodynamic and acoustic components. The acoustic component is more efficient in the generation of the interior noise than the hydrodynamic component. However, the hydrodynamic component is still dominant at low frequencies below approximately 250 Hz since it has low transmission losses near the hydrodynamic critical frequency of the window. The structural modes of the window determine the low-frequency interior tonal noise. The combination of the mode shapes of the window and cavity greatly affects the magnitude distribution of the interior noise.

  15. 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.

  16. Raman spectroscopy for in-situ characterisation of steam generator deposits

    International Nuclear Information System (INIS)

    Rochefort, P.A.; Guzonas, D.A.; Turner, C.W.

    1997-12-01

    This report describes the effort to develop in-situ characterisation of steam generator deposits using remote raman spectroscopy to determine the chemical composition and semi-quantitative measurement of their concentrations. Information on the composition of the deposits is necessary in order to establish the optimal cleaning conditions and procedures. Furthermore, the composition of the deposits also provides information on the conditions that exist within the steam generator and the feedtrain. The raman spectra of the three most common iron oxide phases found in the CANDU deposits (hematite, magnetite and nickel ferrite) are shown

  17. 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

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. A MEMS electret generator with electrostatic levitation for vibration-driven energy-harvesting applications

    International Nuclear Information System (INIS)

    Suzuki, Yuji; Miki, Daigo; Edamoto, Masato; Honzumi, Makoto

    2010-01-01

    In this paper, we propose a passive gap-spacing control method in order to avoid stiction between top and bottom structures in in-plane sensor/actuator/generator applications. A patterned electret using a high-performance perfluoro polymer material is employed to induce a repulsive electrostatic force. An out-of-plane repulsive force is successfully demonstrated with our early prototype, in both air and liquid. By using the present electret-based levitation method to keep the air gap, a MEMS electret generator has been developed for energy-harvesting applications. A dual-phase electrode arrangement is adopted in order to reduce the horizontal electrostatic damping force. With the present prototype, about 0.5 µW is obtained for both phases of the generator, resulting in a total power output of 1.0 µW at an acceleration of 2 g with 63 Hz. With our electromechanical model of the generator, we have confirmed that the model can mimic the response of the generator prototype

  5. 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)

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. DEVELOPMENT OF NEXT-GENERATION DETECTORS AND INSTRUMENTATION FOR PHOTOELECTRON SPECTROSCOPY, DIFFRACTION AND HOLOGRAPHY

    International Nuclear Information System (INIS)

    Charles S. Fadley, Principal Investigator

    2005-01-01

    We have developed a new multichannel detector for use in photoelectron spectroscopy (as well as other types of high-count-rate spectroscopy) that will operate at rates of up to 1 GHz. Such detectors are crucial to the full utilization of the high-brightness radiation generated by third-generation synchrotron radiation sources. In addition, new software and hardware has been developed to permit rapidly and accurately scanning photoelectron spectra that will be accumulated in as little as a 200 micros. A versatile next-generation sample goniometer permitting equally rapid scanning of specimen angles or photon energies for angle-resolved photoemission studies, photoelectron diffraction, and photoelectron holography measurements, and cooling to below 10K has also been designed and constructed. These capabilities have been incorporated into a unique photoelectron spectrometer/diffractometer at the Advanced Light Source of the Lawrence Berkeley National Laboratory; this experimental system includes ultrahigh energy resolution, in situ rotation, variable polarization, and optional spin detection. This overall system is now being used in studies of a variety of problems including magnetic metals and oxides; metal/metal, metal/metal oxide, and metal-oxide/metal-oxide multilayers; and systems exhibiting giant and colossal magnetoresistance

  16. 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 ...

  17. Structure from Dynamics: Vibrational Dynamics of Interfacial Water as a Probe of Aqueous Heterogeneity

    Science.gov (United States)

    2018-01-01

    The structural heterogeneity of water at various interfaces can be revealed by time-resolved sum-frequency generation spectroscopy. The vibrational dynamics of the O–H stretch vibration of interfacial water can reflect structural variations. Specifically, the vibrational lifetime is typically found to increase with increasing frequency of the O–H stretch vibration, which can report on the hydrogen-bonding heterogeneity of water. We compare and contrast vibrational dynamics of water in contact with various surfaces, including vapor, biomolecules, and solid interfaces. The results reveal that variations in the vibrational lifetime with vibrational frequency are very typical, and can frequently be accounted for by the bulk-like heterogeneous response of interfacial water. Specific interfaces exist, however, for which the behavior is less straightforward. These insights into the heterogeneity of interfacial water thus obtained contribute to a better understanding of complex phenomena taking place at aqueous interfaces, such as photocatalytic reactions and protein folding. PMID:29490138

  18. 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.

  19. 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.

  20. 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

  1. Quantum Mechanical Calculations of Vibrational Sum-Frequency-Generation (SFG) Spectra of Cellulose: Dependence of the CH and OH Peak Intensity on the Polarity of Cellulose Chains within the SFG Coherence Domain.

    Science.gov (United States)

    Lee, Christopher M; Chen, Xing; Weiss, Philip A; Jensen, Lasse; Kim, Seong H

    2017-01-05

    Vibrational sum-frequency-generation (SFG) spectroscopy is capable of selectively detecting crystalline biopolymers interspersed in amorphous polymer matrices. However, the spectral interpretation is difficult due to the lack of knowledge on how spatial arrangements of crystalline segments influence SFG spectra features. Here we report time-dependent density functional theory (TD-DFT) calculations of cellulose crystallites in intimate contact with two different polarities: parallel versus antiparallel. TD-DFT calculations reveal that the CH/OH intensity ratio is very sensitive to the polarity of the crystallite packing. Theoretical calculations of hyperpolarizability tensors (β abc ) clearly show the dependence of SFG intensities on the polarity of crystallite packing within the SFG coherence length, which provides the basis for interpretation of the empirically observed SFG features of native cellulose in biological systems.

  2. 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.

  3. Quantitative detection of plasma-generated radicals in liquids by electron paramagnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Tresp, H; Hammer, M U; Winter, J; Reuter, S; Weltmann, K-D

    2013-01-01

    In this paper the qualitative and quantitative detection of oxygen radicals in liquids after plasma treatment with an atmospheric pressure argon plasma jet by electron paramagnetic resonance spectroscopy is investigated. Absolute values for · OH and O 2 ·- radical concentration and their net production rate in plasma-treated liquids are determined without the use of additional scavenging chemicals such as superoxide dismutase (SOD) or mannitol (D-MAN). The main oxygen-centred radical generation in PBS was found to originate from the superoxide radical. It is shown that hidden parameters such as the manufacturer of chemical components could have a big influence on the comparability and reproducibility of the results. Finally, the effect of a shielding gas device for the investigated plasma jet with a shielding gas composition of varying oxygen-to-nitrogen ratio on radical generation after plasma treatment of phosphate-buffered saline solution was investigated. (paper)

  4. Probing a molecular electronic transition by two-colour sum-frequency generation spectroscopy

    International Nuclear Information System (INIS)

    Humbert, C.; Dreesen, L.; Nihonyanagi, S.; Masuda, T.; Kondo, T.; Mani, A.A.; Uosaki, K.; Thiry, P.A.; Peremans, A.

    2003-01-01

    We demonstrate that a new emerging technique, two-colour sum-frequency generation (SFG) spectroscopy, can be used to probe the molecular electronic properties of self-assembled monolayers (SAMs). In the CH spectral range (2800-3200 cm -1 ), we show that the sum-frequency generation signal of a porphyrin alkanethiol derivative adsorbed on Pt(1 1 1) reaches a maximum intensity at ∼435 nm SFG wavelength. This wavelength corresponds to the porphyrin moiety specific π-π* molecular electronic transition which is called the Soret or B band. This resonant behaviour is not observed for 1-dodecanethiol SAMs, which are devoid of molecular electronic transition in the investigated visible spectral range

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Multimodal Broadband Vibrational Sum Frequency Generation (MM-BB-V-SFG) Spectrometer and Microscope.

    Science.gov (United States)

    Lee, Christopher M; Kafle, Kabindra; Huang, Shixin; Kim, Seong H

    2016-01-14

    A broadband sum frequency generation (BB-SFG) spectrometer with multimodal (MM) capabilities was constructed, which could be routinely reconfigured for tabletop experiments in reflection, transmission, and total internal reflection (TIR) geometries, as well as microscopic imaging. The system was constructed using a Ti:sapphire amplifier (800 nm, pulse width = 85 fs, repetition rate = 2 kHz), an optical parameter amplification (OPA) system for production of broadband IR pulses tunable between 1000 and 4000 cm(-1), and two Fabry-Pérot etalons arranged in series for production of narrowband 800 nm pulses. The key feature allowing the MM operation was the nearly collinear alignment of the visible (fixed, 800 nm) and infrared (tunable, 1000-4000 cm(-1)) pulses which were spatially separated. Physical insights discussed in this paper include the comparison of spectral bandwidth produced with 40 and 85 fs pump beams, the improvement of spectral resolution using etalons, the SFG probe volume in bulk analysis, the normalization of SFG signals, the stitching of multiple spectral segments, and the operation in different modes for air/liquid and adsorbate/solid interfaces, bulk samples, as well as spectral imaging combined with principle component analysis (PCA). The SFG spectral features obtained with the MM-BB-SFG system were compared with those obtained with picosecond-scanning-SFG system and high-resolution BB-SFG system (HR-BB-SFG) for dimethyl sulfoxide, α-pinene, and various samples containing cellulose (purified commercial products, Cladophora cell wall, cotton and flax fibers, and onion epidermis cell wall).

  11. 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...

  12. 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

  13. 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.

  14. Flow-induced vibration of steam generator helical tubes subjected to external liquid cross flow and internal two-phase flow

    International Nuclear Information System (INIS)

    Jong Chull Jo; Myung Jo Jhung; Woong Sik Kim; Hho Jung Kim

    2005-01-01

    Full text of publication follows: This paper addresses the potential flow-induced vibration problems in a helically-coiled tube steam generator of integral-type nuclear reactor, of which the tubes are subjected to liquid cross flow externally and multi-phase flow externally. The thermal-hydraulic conditions of both tube side and shell side flow fields are predicted using a general purpose computational fluid dynamics code employing the finite volume element modeling. To get the natural frequency and corresponding mode shape of the helical type tubes with various conditions, a finite element analysis code is used. Based on the results of both helical coiled tube steam generator thermal-hydraulic and coiled tube modal analyses, turbulence-induced vibration and fluid-elastic instability analyses are performed. And then the potential for damages on the tubes due to either turbulence-induced vibration or fluid-elastic instability is assessed. In the assessment, special emphases are put on the detailed investigation for the effects of support conditions, coil diameter, and helix pitch on the modal, vibration amplitude and instability characteristics of tubes, from which a technical information and basis needed for designers and regulatory reviewers can be derived. (authors)

  15. 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.

  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. High Harmonic Generation XUV Spectroscopy for Studying Ultrafast Photophysics of Coordination Complexes

    Science.gov (United States)

    Ryland, Elizabeth S.; Lin, Ming-Fu; Benke, Kristin; Verkamp, Max A.; Zhang, Kaili; Vura-Weis, Josh

    2017-06-01

    Extreme ultraviolet (XUV) spectroscopy is an inner shell technique that probes the M_{2,3}-edge excitation of atoms. Absorption of the XUV photon causes a 3p→3d transition, the energy and shape of which is directly related to the element and ligand environment. This technique is thus element-, oxidation state-, spin state-, and ligand field specific. A process called high-harmonic generation (HHG) enables the production of ultrashort (˜20fs) pulses of collimated XUV photons in a tabletop instrument. This allows transient XUV spectroscopy to be conducted as an in-lab experiment, where it was previously only possible at accelerator-based light sources. Additionally, ultrashort pulses provide the capability for unprecedented time resolution (˜50fs IRF). This technique has the capacity to serve a pivotal role in the study of electron and energy transfer processes in materials and chemical biology. I will present the XUV transient absorption instrument we have built, along with ultrafast transient M_{2,3}-edge absorption data of a series of small inorganic molecules in order to demonstrate the high specificity and time resolution of this tabletop technique as well as how our group is applying it to the study of ultrafast electronic dynamics of coordination complexes.

  20. Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO+ and vibrational resolution in NCO+

    International Nuclear Information System (INIS)

    Holzmeier, Fabian; Lang, Melanie; Fischer, Ingo; Tang, Xiaofeng; Cunha de Miranda, Barbara; Romanzin, Claire; Alcaraz, Christian; Hemberger, Patrick

    2015-01-01

    The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO + was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO + were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X + 3 Σ − ground state was determined to be 11.76 ± 0.02 eV, while for the a +1 Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations

  1. 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.

  2. 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)

  3. Multiphoton electronic-spin generation and transmission spectroscopy in n-type GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Idrish Miah, M., E-mail: m.miah@griffith.edu.a [Department of Physics, University of Chittagong, Chittagong 4331 (Bangladesh)

    2011-01-17

    Multiphoton electronic-spin generation in semiconductors was investigated using differential transmission spectroscopy. The generation of the electronic spins in the semiconductor samples were achieved by multiphoton pumping with circularly polarized light beam and was probed by the spin-resolved transmission of the samples. The electronic spin-polarization of conduction band was estimated and was found to depend on the delay of the probe beam, temperature as well as on the multiphoton pumping energy. The temperature dependence showed a decrease of the spin-polarization with increasing temperature. The electronic spin-polarization was found to depolarize rapidly for multiphoton pumping energy larger than the energy gap of the split-off band to the conduction band. The results were compared with those obtained in one-photon pumping, which shows that an enhancement of the electronic spin-polarization was achieved in multiphoton pumping. The findings resulting from this investigation might have potential applications in opto-spintronics, where the generation of highly polarized electronic spins is required.

  4. Multiphoton electronic-spin generation and transmission spectroscopy in n-type GaAs

    International Nuclear Information System (INIS)

    Idrish Miah, M.

    2011-01-01

    Multiphoton electronic-spin generation in semiconductors was investigated using differential transmission spectroscopy. The generation of the electronic spins in the semiconductor samples were achieved by multiphoton pumping with circularly polarized light beam and was probed by the spin-resolved transmission of the samples. The electronic spin-polarization of conduction band was estimated and was found to depend on the delay of the probe beam, temperature as well as on the multiphoton pumping energy. The temperature dependence showed a decrease of the spin-polarization with increasing temperature. The electronic spin-polarization was found to depolarize rapidly for multiphoton pumping energy larger than the energy gap of the split-off band to the conduction band. The results were compared with those obtained in one-photon pumping, which shows that an enhancement of the electronic spin-polarization was achieved in multiphoton pumping. The findings resulting from this investigation might have potential applications in opto-spintronics, where the generation of highly polarized electronic spins is required.

  5. Influences on the Emissions of Bacterial Plasmas Generated through Nanosecond Laser-Induced Breakdown Spectroscopy

    Science.gov (United States)

    Malenfant, Dylan J.

    In the past decade, laser-induced breakdown spectroscopy has been shown to provide compositional data that can be used for discrimination between bacterial specimens at the strain level. This work demonstrates the viability of this technique in a clinical setting. Studies were conducted to investigate the impact of emissions generated by a nitrocellulose filter paper background on the classification of four species: E. coli, S. epidermidis, M. smegmatis, and P. aeruginosa. Limits of detection were determined as 48+/-12 kCFU per ablation event for new mounting procedures using standard diagnostic laboratory techniques, and a device for centrifuge filtration was designed for sampling from low-titer bacterial suspensions. Plasma emissions from samples grown at biological levels of magnesium, zinc, and glucose were shown not to deviate from controls. A limit of detection for environmental zinc was found to be 11 ppm. Discrimination with heat-killed samples was demonstrated, providing a sterile diagnostic environment.

  6. 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.

  7. IR visible sum-frequency vibrational spectroscopy of Biphenyl-3 methylene thiol monolayer on gold and silver: effect of the visible wavelength on the SFG spectrum

    Science.gov (United States)

    Humbert, C.; Dreesen, L.; Mani, A. A.; Caudano, Y.; Lemaire, J.-J.; Thiry, P. A.; Peremans, A.

    2002-04-01

    We measured IR-visible sum-frequency generation spectra of CH 3-(C 6H 4) 2-(CH 2) 3-S-H (Biphenyl-3) self-assembled monolayers on a silver and a gold substrate. For the latter substrate, we observed different interference patterns between the resonant signal of the CH vibration and the non-resonant contribution of the substrate as a function of the visible beam wavelength. The non-linear response of the gold substrate is enhanced around 480 nm corresponding to the s-d interband transition. Such effect is not observed for the silver substrate the interband transition of which is located out of the investigated visible spectral range of 450-700 nm.

  8. 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.

  9. A Review on the Role of Vibrational Spectroscopy as An Analytical Method to Measure Starch Biochemical and Biophysical Properties in Cereals and Starchy Foods

    Directory of Open Access Journals (Sweden)

    D. Cozzolino

    2014-12-01

    Full Text Available Starch is the major component of cereal grains and starchy foods, and changes in its biophysical and biochemical properties (e.g., amylose, amylopectin, pasting, gelatinization, viscosity will have a direct effect on its end use properties (e.g., bread, malt, polymers. The use of rapid and non-destructive methods to study and monitor starch properties, such as gelatinization, retrogradation, water absorption in cereals and starchy foods, is of great interest in order to improve and assess their quality. In recent years, near infrared reflectance (NIR and mid infrared (MIR spectroscopy have been explored to predict several quality parameters, such as those generated by instrumental methods commonly used in routine analysis like the rapid visco analyser (RVA or viscometers. In this review, applications of both NIR and MIR spectroscopy to measure and monitor starch biochemical (amylose, amylopectin, starch and biophysical properties (e.g., pasting properties will be presented and discussed.

  10. 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.

  11. 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...

  12. Extremely short light pulses: generation; diagnostics, and application in attosecond spectroscopy

    International Nuclear Information System (INIS)

    Iakovlev, V.

    2003-06-01

    The scope of the thesis includes the design of chirped mirrors, as well as theoretical investigations in the fields of high-harmonic generation and laser-dressed Auger decay, the unifying aspect being the presence of extremely short light pulses and physical processes taking place on a femtosecond scale. The main results of the research are the following: 1) It was shown that efficient global optimization of chirped mirrors is possible with an adapted version of the memetic algorithm (also known as hybrid genetic algorithm). 2) The analysis of high-harmonic spectra generated by a few-cycle laser pulse can reveal the electric field of the pulse in the vicinity of its envelope peak. The method developed for this purpose can also be regarded as a method to measure the carrier-envelope phase of laser pulses, which is more robust and has a larger range of applicability compared to the simple analysis of the cut-off region of high-harmonic spectra. 3) A quantum theory of time-resolved Auger spectroscopy was developed. Based on the essential states method, closed-form expressions for probability amplitudes were derived. The theory lays the foundation for the interpretation of experiments that probe electronic motion during atomic excitation, deexcitation, and ionization. (author)

  13. Mobile Charge Generation Dynamics in P3HT:PCBM Observed by Time-Resolved Terahertz Spectroscopy

    DEFF Research Database (Denmark)

    Cooke, D. G.; Krebs, Frederik C; Jepsen, Peter Uhd

    2012-01-01

    Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale.......Ultra-broadband time-resolved terahertz spectroscopy is used to examine the sub-ps conductivity dynamics of a conjugated polymer bulk heterojunction film P3HT:PCBM. We directly observe mobile charge generation dynamics on a sub-100 fs time scale....

  14. 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

  15. 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.

  16. Influence of bearing pre-load coefficient on shaft vibration and pad temperature in a hydroturbine generator unit. A case study

    Energy Technology Data Exchange (ETDEWEB)

    Feng Fuzhou; Chu Fulei; Guo Dan; Lu Wenxiu [Tsinghua Univ., Beijing, BJ (China). Dept. of Precision Instruments

    2001-07-01

    From data collected by an online condition monitoring and fault diagnosis system, a higher pad temperature at the upper guide bearing in a pumped storage power generator unit installed in Guangdong province(GPSPS), China, was found. And also a relatively intensive shaft vibration occurred at the lower guide bearing. By calculating the Reynolds equation and viscosity-temperature equation of the lubricant, a curve between the pre-load coefficient and the increment of pad temperature is obtained, which shows that the larger, the pre-load coefficient, the bigger, the increment of pad temperature. For a practical unit in GPSPS, by employing Transfer matrix method and Wilson-{theta} method to analyze shaft vibration at different pre-load coefficients of the whole bearing or ''pad pair'' bearings, the results show that the larger the pre-load coefficient is, the smaller the vibration amplitude is, the shorter the time for vibration to become steady is. And an uneven pre-load coefficient of the ''pad pair'' bearings will cause shaft orbit from a circle to an ellipse whose long axes is at the direction of the ''pad pair'' with the lowest pre-load coefficient. Finally, reasons of higher pad temperature of the upper guide bearing and larger shaft vibration at the lower guide bearing are due to the inconsistent relation of bearing assembling clearance or pre-load coefficient of the upper and lower guide bearing, and also due to the too small, uneven pre-load coefficient of ''pad pair'' bearings. After a scheme for adjusting the bearing clearance is given, data measured show that the analysis and simulation methods are correct and the adjustment scheme to the assembling clearance of the upper and lower guide bearings is feasible and can be used to guide the field maintenance conveniently. (orig.)

  17. Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    C. J. Ebben

    2011-10-01

    Full Text Available We present the vibrational sum frequency generation spectra of organic particles collected in a boreal forest in Finland and a tropical forest in Brazil. These spectra are compared to those of secondary organic material produced in the Harvard Environmental Chamber. By comparing coherent vibrational spectra of a variety of terpene and olefin reference compounds, along with the secondary organic material synthesized in the environmental chamber, we show that submicron aerosol particles sampled in Southern Finland during HUMPPA-COPEC-2010 are composed to a large degree of material similar in chemical composition to synthetic α-pinene-derived material. For material collected in Brazil as part of AMAZE-08, the organic component is found to be chemically complex in the coarse mode but highly uniform in the fine mode. When combined with histogram analyses of the isoprene and monoterpene abundance recorded during the HUMPPA-COPEC-2010 and AMAZE-08 campaigns, the findings presented here indicate that if air is rich in monoterpenes, submicron-sized secondary aerosol particles that form under normal OH and O3 concentration levels can be described in terms of their hydrocarbon content as being similar to α-pinene-derived model secondary organic aerosol particles. If the isoprene concentration dominates the chemical composition of organic compounds in forest air, then the hydrocarbon component of secondary organic material in the submicron size range is not simply well-represented by that of isoprene-derived model secondary organic aerosol particles but is more complex. Throughout the climate-relevant size range of the fine mode, however, we find that the chemical composition of the secondary organic particle material from such air is invariant with size, suggesting that the particle growth does not change the chemical composition of the hydrocarbon component of the particles in a significant way.

  18. Final design and progress of WEAVE : the next generation wide-field spectroscopy facility for the William Herschel Telescope

    NARCIS (Netherlands)

    Dalton, Gavin; Trager, Scott; Abrams, Don Carlos; Bonifacio, Piercarlo; Aguerri, J. Alfonso L.; Middleton, Kevin; Benn, Chris; Dee, Kevin; Sayède, Frédéric; Lewis, Ian; Pragt, Johannes; Pico, Sergio; Walton, Nic; Rey, Jeurg; Allende Prieto, Carlos; Peñate, José; Lhome, Emilie; Agócs, Tibor; Alonso, José; Terrett, David; Brock, Matthew; Gilbert, James; Schallig, Ellen; Ridings, Andy; Guinouard, Isabelle; Verheijen, Marc; Tosh, Ian; Rogers, Kevin; Lee, Martin; Steele, Iain; Stuik, Remko; Tromp, Niels; Jaskó, Attila; Carrasco, Esperanza; Farcas, Szigfrid; Kragt, Jan; Lesman, Dirk; Kroes, Gabby; Mottram, Chris; Bates, Stuart; Rodriguez, Luis Fernando; Gribbin, Frank; Delgado, José Miguel; Herreros, José Miguel; Martin, Carlos; Cano, Diego; Navarro, Ramon; Irwin, Mike; Lewis, Jim; Gonzalez Solares, Eduardo; Murphy, David; Worley, Clare; Bassom, Richard; O'Mahoney, Neil; Bianco, Andrea; Zurita, Christina; ter Horst, Rik; Molinari, Emilio; Lodi, Marcello; Guerra, José; Martin, Adrian; Vallenari, Antonella; Salasnich, Bernardo; Baruffolo, Andrea; Jin, Shoko; Hill, Vanessa; Smith, Dan; Drew, Janet; Poggianti, Bianca; Pieri, Mat; Dominquez Palmero, Lillian; Farina, Cecilia

    2016-01-01

    We present the Final Design of the WEAVE next-generation spectroscopy facility for the William Herschel Telescope (WHT), together with a status update on the details of manufacturing, integration and the overall project schedule now that all the major fabrication contracts are in place. We also

  19. Final design and progress of WEAVE: the next generation wide-field spectroscopy facility for the William Herschel Telescope

    NARCIS (Netherlands)

    Dalton, Gavin; Trager, Scott; Abrams, Don Carlos; Bonifacio, Piercarlo; Aguerri, J. Alfonso L.; Middleton, Kevin; Benn, Chris; Dee, Kevin; Sayède, Frédéric; Lewis, Ian; Pragt, Johannes; Pico, Sergio; Walton, Nic; Rey, Jeurg; Allende Prieto, Carlos; Peñate, José; Lhome, Emilie; Agócs, Tibor; Alonso, José; Terrett, David; Brock, Matthew; Gilbert, James; Schallig, Ellen; Ridings, Andy; Guinouard, Isabelle; Verheijen, Marc; Tosh, Ian; Rogers, Kevin; Lee, Martin; Steele, Iain; Stuik, Remko; Tromp, Niels; Jaskó, Attila; Carrasco, Esperanza; Farcas, Szigfrid; Kragt, Jan; Lesman, Dirk; Kroes, Gabby; Mottram, Chris; Bates, Stuart; Rodriguez, Luis Fernando; Gribbin, Frank; Delgado, José Miguel; Herreros, José Miguel; Martin, Carlos; Cano, Diego; Navarro, Ramon; Irwin, Mike; Lewis, Jim; Gonzalez Solares, Eduardo; Murphy, David; Worley, Clare; Bassom, Richard; O'Mahoney, Neil; Bianco, Andrea; Zurita, Christina; ter Horst, Rik; Molinari, Emilio; Lodi, Marcello; Guerra, José; Martin, Adrian; Vallenari, Antonella; Salasnich, Bernardo; Baruffolo, Andrea; Jin, Shoko; Hill, Vanessa; Smith, Dan; Drew, Janet; Poggianti, Bianca; Pieri, Mat; Dominquez Palmero, Lillian; Farina, Cecilia

    2016-01-01

    We present the Final Design of the WEAVE next-generation spectroscopy facility for the William Herschel Telescope (WHT), together with a status update on the details of manufacturing, integration and the overall project schedule now that all the major fabrication contracts are in place. We also

  20. Project overview and update on WEAVE: the next generation wide-field spectroscopy facility for the William Herschel Telescope

    NARCIS (Netherlands)

    Dalton, Gavin; Trager, Scott; Abrams, Don Carlos; Bonifacio, Piercarlo; López Aguerri, J. Alfonso; Middleton, Kevin; Benn, Chris; Dee, Kevin; Sayède, Frédéric; Lewis, Ian; Pragt, Johan; Pico, Sergio; Walton, Nic; Rey, Juerg; Allende Prieto, Carlos; Peñate, José; Lhome, Emilie; Agócs, Tibor; Alonso, José; Terrett, David; Brock, Matthew; Gilbert, James; Ridings, Andy; Guinouard, Isabelle; Verheijen, Marc A.W.; Tosh, Ian; Rogers, Kevin; Steele, Iain; Stuik, Remko; Tromp, Neils; Jasko, Attila; Kragt, Jan; Lesman, Dirk; Mottram, Chris; Bates, Stuart; Gribbin, Frank; Rodriguez, Luis Fernando; Delgado, José M.; Martin, Carlos; Cano, Diego; Navarro, Ramón; Irwin, Mike; Lewis, Jim; Gonzalez Solares, Eduardo; O'Mahony, Neil; Bianco, Andrea; Zurita, Christina; ter Horst, Rik; Molinari, Emilio; Lodi, Marcello; Guerra, José; Vallenari, Antonella; Baruffolo, Andrea

    We present an overview of and status report on the WEAVE next-generation spectroscopy facility for the William Herschel Telescope (WHT). WEAVE principally targets optical ground-based follow up of upcoming ground-based (LOFAR) and space-based (Gaia) surveys. WEAVE is a multi-object and multi-IFU

  1. 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.

  2. Generation of Small Single Domain Nanobody Binders for Sensitive Detection of Testosterone by Electrochemical Impedance Spectroscopy.

    Science.gov (United States)

    Li, Guanghui; Zhu, Min; Ma, Lu; Yan, Junrong; Lu, Xiaoling; Shen, Yanfei; Wan, Yakun

    2016-06-08

    A phage display library of variable domain of the heavy chain only antibody or nanobody (Nb) was constructed after immunizing a bactrian camel with testosterone. With the smaller molecular size (15 kDa), improved solubility, good stability, high affinity, specificity, and lower immunogenicity, Nbs are a promising tool in the next generation of diagnosis and medical applications. Testosterone is a reproductive hormone, playing an important role in normal cardiac function and being the highly predictive marker for many diseases. Herein, a simple and sensitive immunosensor based on electrochemical impedance spectroscopy (EIS) and Nbs was successfully developed for the determination of testosterone. We successfully isolated the antitestosterone Nbs from an immune phage display library. Moreover, one of the Nbs was biotinylated according to in vivo BirA system, which showed the highest production yield and the most stable case. Further, the EIS immunosensor was set up for testosterone detection by applying the biotinylated antitestosterone Nb. As a result, the biosensor exhibited a linear working range from 0.05 to 5 ng mL(-1) with a detection limit of 0.045 ng mL(-1). In addition, the proposed immunosensor was successfully applied in determining testosterone in serum samples. In conclusion, the proposed immunosensor revealed high specificity of testosterone detection and showed as a potential approach for sensitive and accurate diagnosis of testosterone.

  3. Charge generation in organic solar cell materials studied by terahertz spectroscopy

    KAUST Repository

    Scarongella, M.

    2015-09-09

    We have investigated the photophysics in neat films of conjugated polymer PBDTTPD and its blend with PCBM using terahertz time-domain spectroscopy. This material has very high efficiency when used in organic solar cells. We were able to identify a THz signature for bound excitons in neat PBDTTPD films, pointing to important delocalization in those excitons. Then, we investigated the nature and local mobility (orders of magnitude higher than bulk mobility) of charges in the PBDTTPPD:PCBM blend as a function of excitation wavelength, fluence and pump-probe time delay. At low pump fluence (no bimolecular recombination phenomena), we were able to observe prompt and delayed charge generation components, the latter originating from excitons created in neat polymer domains which, thanks to delocalization, could reach the PCBM interface and dissociate to charges on a time scale of 1 ps. The nature of the photogenerated charges did not change between 0.5 ps and 800 ps after photo-excitation, which indicated that the excitons split directly into relatively free charges on an ultrafast time scale. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  4. 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.

  5. Applications of photon-in, photon-out spectroscopy with third-generation, synchrotron-radiation sources

    International Nuclear Information System (INIS)

    Lindle, D.W.; Perera, R.C.C.

    1991-01-01

    This report discusses the following topics: Mother nature's finest test probe; soft x-ray emission spectroscopy with high-brightness synchrotron radiation sources; anisotropy and polarization of x-ray emission from atoms and molecules; valence-hole fluorescence from molecular photoions as a probe of shape-resonance ionization: progress and prospects; structural biophysics on third-generation synchrotron sources; ultra-soft x-ray fluorescence-yield XAFS: an in situ photon-in, photon-out spectroscopy; and x-ray microprobe: an analytical tool for imaging elemental composition and microstructure

  6. 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.

  7. 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.

  8. 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.

  9. Nonlinear generation of non-acoustic modes by low-frequency sound in a vibrationally relaxing gas

    International Nuclear Information System (INIS)

    Perelomova, A.

    2010-01-01

    Two dynamic equations referring to a weakly nonlinear and weakly dispersive flow of a gas in which molecular vibrational relaxation takes place, are derived. The first one governs an excess temperature associated with the thermal mode, and the second one describes variations in vibrational energy. Both quantities refer to non-wave types of gas motion. These variations are caused by the nonlinear transfer of acoustic energy into thermal mode and internal vibrational degrees of freedom of a relaxing gas. The final dynamic equations are instantaneous; they include a quadratic nonlinear acoustic source, reflecting the nonlinear character of interaction of low-frequency acoustic and non-acoustic motions of the fluid. All types of sound, periodic or aperiodic, may serve as an acoustic source of both phenomena. The low-frequency sound is considered in this study. Some conclusions about temporal behavior of non-acoustic modes caused by periodic and aperiodic sound are made. Under certain conditions, acoustic cooling takes place instead of heating. (author)

  10. Infrared spectroscopy of flavones and flavonols. Reexamination of the hydroxyl and carbonyl vibrations in relation to the interactions of flavonoids with membrane lipids

    Science.gov (United States)

    Baranović, Goran; Šegota, Suzana

    2018-03-01

    Detailed vibrational assignments for twelve flavonoids (seven flavones (flavone, 3- and 5-hydroxyflavone, chrysin, apigenin, fisetin and luteolin) and five flavonols (galangin, kaempferol, quercetin, morin and myricetin)) have been made based on own and reported experimental data and calculations at the B3LYP/6-31 + G(d,p) level of theory. All the molecules are treated in a uniform way by using the same set of redundancy-free set of internal coordinates. A generalized harmonic mode mixing is used to corroborate the vibrational characteristics of this important class of molecules. Each flavonoid molecule can be treated from the vibrational point of view as made of relatively weakly coupled chromone and phenyl part. It has been shown that the strongest band around 1600 cm- 1 need not be attributable to the Cdbnd O stretching. The way the vibrations of any of the hydroxyl groups are mixed with ring vibrations and vibrations of other neighboring hydroxyl groups is rather involved. This imposes severe limitations on any attempt to describe normal modes of a flavonol in terms of hydroxyl or carbonyl group vibrations. The role of water molecules in the appearance of flavonoid IR spectra is emphasized. Knowing for the great affinity of phosphate groups in lipids towards water, the immediate consequence is a reasonable assumption that flavonoid lipid interactions is mediated by water.

  11. Power-Generation Characteristics After Vibration and Thermal Stresses of Thermoelectric Unicouples with CoSb3/Ti/Mo(Cu) Interfaces

    Science.gov (United States)

    Bae, Kwang Ho; Choi, Soon-Mok; Kim, Kyung-Hun; Choi, Hyoung-Seuk; Seo, Won-Seon; Kim, Il-Ho; Lee, Soonil; Hwang, Hae Jin

    2015-06-01

    Reliability tests for thermoelectric unicouples were carried out to investigate the adhesion properties of CoSb3/Ti/Mo(Cu) interfaces. The n-type In0.25 Co3.95Ni0.05Sb12 and p-type In0.25Co3FeSb12 bulks were prepared for fabricating a thermoelectric unicouple (one p- n couple) by an induction melting and a spark plasma sintering process. Mo-Cu alloy was selected as an electrode for the unicouples due to its high melting temperature and proper work function value. Many thermoelectric unicouples with the CoSb3/Ti/Mo(Cu) interfaces were fabricated with the proper brazing materials by means of a repeated firing process. Reliability of the unicouples with the interfaces was evaluated by a vibration test and a thermal cycling test. After the thermal cycling and vibration tests, the power-generation characteristics of the unicouples were compared with the unicouples before the tests. Even after the vibration test, electrical power with a power density of 0.5 W/cm2 was generated. The Ti-interlayer is considered as a possible candidate for making a reliable unicouple with high adhesion strength. With the thermal cycling test, the resistance of the unicouple increased and the electrical power from the unicouple decreased. A failure mode by the thermal cycling test was ascribed to a complex effect of micro-cracks originated from the thermal stress and oxidation problem of the thermoelectric materials; that is, a thick oxide layer more than 300 μm was detected after a high-temperature durability test of n-type In0.25Co3.95Ni0.05Sb12 material at 773 K in air for 7 days.

  12. Vibration in car repair work.

    Science.gov (United States)

    Hansson, J E; Eklund, L; Kihlberg, S; Ostergren, C E

    1987-03-01

    The main objective of the study was to find efficient hand tools which caused only minor vibration loading. Vibration measurements were carried out under standardised working conditions. The time during which car body repairers in seven companies were exposed to vibration was determined. Chisel hammers, impact wrenches, sanders and saws were the types of tools which generated the highest vibration accelerations. The average daily exposure at the different garages ranged from 22 to 70 min. The risk of vibration injury is currently rated as high. The difference between the highest and lowest levels of vibration was considerable in most tool categories. Therefore the choice of tool has a major impact on the magnitude of vibration exposure. The importance of choosing the right tools and working methods is discussed and a counselling service on vibration is proposed.

  13. Flow-induced vibration analysis of Three Mile Island Unit-2 once-through steam generator tubes. Volume 1. Final report

    International Nuclear Information System (INIS)

    Johnson, J.R.; Brown, J.C.; Harris, C.E.; McGuinn, E.J.; Simonis, J.C.; Thoren, D.E.

    1981-06-01

    Tube responses to flow-induced vibration were measured in the top two spans and the tenth span in the B once-through steam generator at Three Mile Island, Unit 2. This program evaluated the effects of flow-induced biration of OTSG tubes during steady-state and transient operation. Twenty-three tubes were instrumented with accelerometers and strain gages in tubes located along the open lane, in the bundle, and at the tenth span. Tube displacements, frequencies, dynamic strains, and mode shapes were determined during steady-state and transient operation. Pressure sensors were installed in the OTSG to measure pressure fluctuations and plant parameters, which were recorded for correlation with tube response. Data analysis results indicate that the steady-state tube response increases with increasing reactor power, with the maximum response (12 mils peak to peak at midspan) at the outer perimeter of the generator in the 16th span

  14. Ultrafast vibrational spectroscopy (2D-IR) of CO{sub 2} in ionic liquids: Carbon capture from carbon dioxide’s point of view

    Energy Technology Data Exchange (ETDEWEB)

    Brinzer, Thomas; Berquist, Eric J.; Ren, Zhe; Dutta, Samrat; Johnson, Clinton A.; Krisher, Cullen S.; Lambrecht, Daniel S.; Garrett-Roe, Sean, E-mail: sgr@pitt.edu [Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260 (United States)

    2015-06-07

    The CO{sub 2}ν{sub 3} asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO{sub 2} is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C{sub 4}C{sub 1}im][X], where [X]{sup −} is the anion from the series hexafluorophosphate (PF{sub 6}{sup −}), tetrafluoroborate (BF{sub 4}{sup −}), bis-(trifluoromethyl)sulfonylimide (Tf{sub 2}N{sup −}), triflate (TfO{sup −}), trifluoroacetate (TFA{sup −}), dicyanamide (DCA{sup −}), and thiocyanate (SCN{sup −})). In the ionic liquids studied, the ν{sub 3} center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO{sub 2} and from CO{sub 2} to the cation. The charge transfer drives geometrical distortion of CO{sub 2}, which in turn changes the ν{sub 3} frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν{sub 2} and ν{sub 3} normal modes of CO{sub 2}. Thermal fluctuations in the ν{sub 2} population stochastically modulate the ν{sub 3} frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO{sub 2}. The results suggest that the picosecond dynamics of CO{sub 2} are gated by local diffusion of anions and cations.

  15. 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.

  16. Vibration mixer

    Energy Technology Data Exchange (ETDEWEB)

    Alekhin, S.A.; Chernov, V.S.; Denisenko, V.V.; Gorodnyanskiy, I.F.; Prokopov, L.I.; Tikhonov, Yu.P.

    1983-01-01

    The vibration mixer is proposed which contains a housing, vibration drive with rod installed in the upper part of the mixing mechanism made in the form of a hollow shaft with blades. In order to improve intensity of mixing and dispersion of the mud, the shaft with the blades is arranged on the rod of the vibrator and is equipped with a cam coupling whose drive disc is attached to the vibration rod. The rod is made helical, while the drive disc of the cam coupling is attached to the helical surface of the rod. In addition, the vibration mixer is equipped with perforated discs installed on the ends of the rods.

  17. Generation of pulsed far-infrared radiation and its application for far-infrared time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, Yasuhiro [Tohoku Univ., Sendai (Japan). Faculty of Engineering

    1996-07-01

    So-called time-resolved spectroscopy technique has been used from old time as the means for studying the dynamic optical property, light-induced reaction and so on of matters. As an example, there is the method called pump and probe, and here, the wavelength of this probe light is the problem. If the object energy region is limited to about 0.1 eV, fast time-resolved spectroscopy is feasible relatively easily. However, energy region is extended to low energy region, the light source which is available as the pulsed probe light having sufficient intensity is limited. In this paper, the attempt of time-resolved spectroscopy utilizing coherent radiation, which has ended in failure, and the laser pulse-induced far-infrared radiation which can be utilized as new far-infrared probe light are reported. The reason why far-infrared radiation is used is explained. The attempt of time-resolved spectroscopy using NaCl crystals is reported on the equipment, the method of measuring absorption spectra and the results. Laser pulse-induced far-infrared radiation and the method of generating it are described. The multi-channel detector for far-infrared radiation which was made for trial is shown. (K.I.)

  18. Next generation laser-based standoff spectroscopy techniques for Mars exploration.

    Science.gov (United States)

    Gasda, Patrick J; Acosta-Maeda, Tayro E; Lucey, Paul G; Misra, Anupam K; Sharma, Shiv K; Taylor, G Jeffrey

    2015-01-01

    In the recent Mars 2020 Rover Science Definition Team Report, the National Aeronautics and Space Administration (NASA) has sought the capability to detect and identify elements, minerals, and most importantly, biosignatures, at fine scales for the preparation of a retrievable cache of samples. The current Mars rover, the Mars Science Laboratory Curiosity, has a remote laser-induced breakdown spectroscopy (LIBS) instrument, a type of quantitative elemental analysis, called the Chemistry Camera (ChemCam) that has shown that laser-induced spectroscopy instruments are not only feasible for space exploration, but are reliable and complementary to traditional elemental analysis instruments such as the Alpha Particle X-Ray Spectrometer. The superb track record of ChemCam has paved the way for other laser-induced spectroscopy instruments, such as Raman and fluorescence spectroscopy. We have developed a prototype remote LIBS-Raman-fluorescence instrument, Q-switched laser-induced time-resolved spectroscopy (QuaLITy), which is approximately 70 000 times more efficient at recording signals than a commercially available LIBS instrument. The increase in detection limits and sensitivity is due to our development of a directly coupled system, the use of an intensified charge-coupled device image detector, and a pulsed laser that allows for time-resolved measurements. We compare the LIBS capabilities of our system with an Ocean Optics spectrometer instrument at 7 m and 5 m distance. An increase in signal-to-noise ratio of at least an order of magnitude allows for greater quantitative analysis of the elements in a LIBS spectrum with 200-300 μm spatial resolution at 7 m, a Raman instrument capable of 1 mm spatial resolution at 3 m, and bioorganic fluorescence detection at longer distances. Thus, the new QuaLITy instrument fulfills all of the NASA expectations for proposed instruments.

  19. Interrogating the vibrational relaxation of highly excited polyatomics with time-resolved diode laser spectroscopy: C6H6, C6D6, and C6F6+CO2

    International Nuclear Information System (INIS)

    Sedlacek, A.J.; Weston, R.E. Jr.; Flynn, G.W.

    1991-01-01

    The vibrational relaxation of highly excited ground state benzene, benzene d 6 , and hexafluorobenzene by CO 2 has been investigated with high resolution diode laser spectroscopy. The vibrationally hot polyatomics are formed by single photon 248 nm excitation to the S 1 state followed by rapid radiationless transitions. It has been found that in all cases less than 1% of the energy initially present in the polyatomics is deposited into the high frequency mode of CO 2 (ν 3 ). An investigation of the CO 2 (00 0 1) nascent rotational distribution under single collision conditions reveals that very little rotational excitation accompanies vibrational energy transfer to the ν 3 mode. The CO 2 (ν 3 ) rotational states can be described by temperatures, T rot , as follows: C 6 H 6 , T rot =360±30 K; C 6 D 6 , T rot =350±35 K and C 6 F 6 , T rot =340±23 K. An estimate of left-angle ΔE right-angle ν3 , the mean energy transferred to the CO 2 ν 3 mode per collision, suggests that as the availability of low frequency modes in the excited molecule increases, less energy is deposited into the high frequency mode of CO 2 . Finally, evidence is presented suggesting that even at moderate laser fluences, the two-photon ionization of benzene can lead to substantial CO 2 ν 3 excitation via electron+CO 2 inelastic collisions

  20. Study of confinement and sliding friction of fluids using sum frequency generation spectroscopy

    Science.gov (United States)

    Nanjundiah, Kumar

    2007-12-01

    Friction and wear are important technologically. Tires on wet roads, windshield wipers and human joints are examples where nanometer-thick liquids are confined between flexible-rigid contact interfaces. Fundamental understanding of the structure of these liquids can assist in the design of products such as artificial joints and lubricants for Micro-electromechanical systems [MEMS]. Prior force measurements have suggested an increase in apparent viscosity of confined liquid and sometimes solid-like responses. But, these have not given the state of molecules under confinement. In the present study, we have used a surface sensitive, non-linear optical technique (infrared-visible sum frequency generation spectroscopy [SFG]) to investigate molecular structure at hidden interfaces. SFG can identify chemical groups, concentration and orientation of molecules at an interface. A friction cell was developed to study sliding of a smooth elastomeric lens against a sapphire surface. Experiments were done with dry sliding as well as lubricated sliding in the presence of linear alkane liquids. SFG spectra at the alkane/sapphire interface revealed ordering of the confined alkane molecules. These were more ordered than alkane liquid, but less ordered than alkane crystal. Cooling of the confined alkane below its melting temperature [TM] led to molecular orientation that was different from that of bulk crystal next to a sapphire surface. Molecules were oriented with their symmetry axis parallel to the surface normal. In addition, the melting temperature [Tconf] under confinement for a series of linear alkanes (n =15--27) showed a surprising trend. Intermediate molecular weights showed melting point depression. The T conf values suggested that melting started at the alkane/sapphire interface. In another investigation, confinement of water between an elastomeric PDMS lens and sapphire was studied. SFG spectra at the sapphire/water/PDMS interface revealed a heterogeneous morphology. The

  1. Interaction of nanodiamond with in situ generated sp-carbon chains probed by Raman spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Zukalová, Markéta; Kalbáč, Martin; Osawa, E.; Dunsch, L.

    2006-01-01

    Roč. 44, č. 14 (2006), s. 3113-3116 ISSN 0008-6223 R&D Projects: GA AV ČR IAA4040306; GA MŠk LC510 Grant - others:NEDO International Grant(XE) 20041T081 Institutional research plan: CEZ:AV0Z40400503 Keywords : carbyne * diamond * Raman spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 3.884, year: 2006

  2. Vibrational spectroscopy of the G...C base pair: Experiment, harmonic and anharmonic calculations, and the nature of the anharmonic couplings

    Czech Academy of Sciences Publication Activity Database

    Brauer, B.; Gerber, R. B.; Kabeláč, Martin; Hobza, Pavel; Bakker, J. M.; Abo-Riziq, A.; Vries de, M. S.

    2005-01-01

    Roč. 109, - (2005), s. 6974-6984 ISSN 1089-5639 Grant - others:NSF(US) CHE-0244341 Institutional research plan: CEZ:AV0Z40550506 Keywords : nucleic acids bases * vibrational spectrum * frequencies anharmonicity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.898, year: 2005

  3. X-ray absorption spectroscopy in the keV range with laser generated high harmonic radiation

    International Nuclear Information System (INIS)

    Seres, Enikoe; Seres, Jozsef; Spielmann, Christian

    2006-01-01

    By irradiating He and Ne atoms with 3 mJ, 12 fs, near infrared laser pulses from a tabletop laser system, the authors generated spatially and temporally coherent x rays up to a photon energy of 3.5 keV. With this source it is possible to use high-harmonic radiation for x-ray absorption spectroscopy in the keV range. They were able to clearly resolve the L absorption edges of titanium and copper and the K edges of aluminum and silicon. From the fine structure of the x-ray absorption they estimated the interatomic distances

  4. Linking structure and vibrational mode coupling using high-resolution infrared spectroscopy: A comparison of gauche and trans 1-chloro-2-fluoroethane

    Science.gov (United States)

    Miller, C. Cameron; Stone, Stephen C.; Philips, Laura A.

    1995-01-01

    The high-resolution infrared spectrum of 1-chloro-2-fluoroethane in a molecular beam was collected over the 2975-2994 cm-1 spectral region. The spectral region of 2975-2981 cm-1 contains a symmetric C-H stretching vibrational band of the gauche conformer containing the 35Cl isotope. The spectral region of 2985-2994 cm-1 contains three vibrational bands of the trans conformer. Two of the three bands are assigned as an antisymmetric C-H stretch of each of the two different chlorine isotopes. The third band is assigned as a symmetric C-H stretch of the 35Cl isotope. The gauche conformer of 1-chloro-2-fluoroethane showed doublet patterns similar to those previously observed in 1,2-difluoroethane. The model for 1,2-difluoroethane is further refined in the present work. These refinements suggest that the coupling dark state in 1,2-difluoroethane is composed of 1 quantum C-H bend, 1 quantum C-C stretch, and 12 quanta of torsion. For 1-chloro-2-fluoroethane the dark state could not be identified due to a small data set. The trans conformer of 1-chloro-2-fluoroethane showed no evidence of mode coupling in the three vibrational bands. Including 2-fluoroethanol in this series of molecules, the extent of vibrational mode coupling did not correlate with the density of states available for coupling. Therefore, density of states alone is insufficient to explain the observed trend. A correlation was observed between the degree of intramolecular interaction and vibrational mode coupling.

  5. Vibrational spectrum of the K-590 intermediate in the bacteriorhodopsin photocycle at room temperature: picosecond time-resolved resonance coherent anti-Raman spectroscopy

    Science.gov (United States)

    Ujj, L.; Jäger, F.; Popp, A.; Atkinson, G. H.

    1996-12-01

    The vibrational spectrum of the K-590 intermediate, thought to contribute significantly to the energy storage and transduction mechanism in the bacteriorhodopsin (BR) photocycle, is measured at room temperature using picosecond time-resolved resonance coherent anti-Stokes Raman scattering (PTR/CARS). The room-temperature BR photocycle is initiated by the 3 ps, 570 nm excitation of the ground-state species, BR-570, prepared in both H 2O and D 2O suspensions of BR. PTR/CARS data, recorded 50 ps after BR-570 excitation, at which time only BR-570 and K-590 are present, have an excellent S/N which provides a significantly more detailed view of the K-590 vibrational degrees of freedom than previously available. Two picosecond (6 ps FWHM) laser pulses, ω1 (633.4 nm) and ωS (675-700 nm), are used to record PTR/CARS data via electronic resonance enhancement in both BR-570 and K-590, each of which contains a distinct retinal structure (assigned as 13- rans, 15- anti, 13- cis, respectively). To obtain the vibrational spectrum of K-590 separately, the PTR/CARS spectra from the mixture of isomeric retinals is quantitatively analyzed in terms of third-order susceptibility ( η(3)) relationships. PTR/CARS spectra of K-590 recorded from both H 2O and D 2O suspensions of BR are compared with the analogous vibrational data obtained via spontaneous resonance Raman (RR) scattering at both low (77 K) and room temperature. Analyses of these vibrational spectra identify temperature-dependent effects and changes assignable to the substitution of deuterium at the Schiff-base nitrogen not previously reported.

  6. Vibration damping method and apparatus

    Science.gov (United States)

    Redmond, James M.; Barney, Patrick S.; Parker, Gordon G.; Smith, David A.

    1999-01-01

    The present invention provides vibration damping method and apparatus that can damp vibration in more than one direction without requiring disassembly, that can accommodate varying tool dimensions without requiring re-tuning, and that does not interfere with tool tip operations and cooling. The present invention provides active dampening by generating bending moments internal to a structure such as a boring bar to dampen vibration thereof.

  7. High-resolution inner-shell spectroscopies of free atoms and molecules using soft-x-ray beamlines at the third-generation synchrotron radiation sources

    International Nuclear Information System (INIS)

    Ueda, Kiyoshi

    2003-01-01

    This article reviews the current status of inner-shell spectroscopies of free atoms and molecules using high-resolution soft-x-ray monochromators installed in the soft-x-ray beamlines at the third-generation synchrotron radiation facilities. Beamlines and endstations devoted to atomic and molecular inner-shell spectroscopies and various types of experimental techniques, such as ion yield spectroscopy, resonant photoemission spectroscopy and multiple-coincidence momentum imaging, are described. Experimental results for K-shell excitation of Ne, O K-shell excitation of H 2 O and CO 2 , C K-shell excitation and ionization of CO 2 and B K-shell excitation of BF 3 , obtained at beamline 27SU of SPring-8 in Japan, are discussed as examples of atomic and molecular inner-shell spectroscopies using the third-generation synchrotron radiation sources. (topical review)

  8. Design of a generator of harmonic vibrations for rotary unbalance; Diseno de un generador de vibraciones armonicas por desbalance rotatorio

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez Vazquez, Ely Edmundo [Grupo de Investigacion Aplicada, Queretaro, Queretaro (Mexico); Silva Navarro, Gerardo [Cinvestav, IPN, Mexico, D.F. (Mexico); Zuniga Osorio, Helen Janeth [CIATEQ, Queretaro, Queretaro (Mexico)

    2007-11-15

    In this paper is presented the experimental development of an integral system for the monitoring and acquisition of involved physical variables in the performance analysis of the turbo-machinery. The integral system has been denominated SMD Turbo (System of Monitoring and Diagnosis for turbo-machinery) and has as fundamental intention to realize the analysis and diagnosis (on the basis of mathematical and graphical tools) of the performance of a machine through the physical measurement of physical variables such as pressure, temperature and vibration. The system is able to realize the analysis of the information in real time and to store it for its later processing of diagnosis by means of specialized software with which the calculations of the performance will be able to be realized. Preliminary results of the proposal are presented that confirm the viability of the proposal. [Spanish] En este trabajo se presenta el desarrollo experimental de un sistema integral para el monitoreo y adquisicion de variables fisicas involucradas en el analisis del rendimiento de la turbomaquinaria. El sistema integral se ha denominado SMD Turbo (Sistema de Monitoreo y Diagnostico para trubomaquinaria) y tiene como proposito fundamental realizar el analisis y diagnostico (en base a herramientas matematicas y graficas) del rendimiento de la turbo maquina a traves de la medicion de variable fisicas como por ejemplo, presion, temperatura y vibracion. El sistema es capaz de realizar el analisis de la informacion en tiempo real y almacenarla para su posterior proceso de diagnostico mediante un software especializado con el cual se podran realizar los calculos del rendimiento. Se presentan resultados preliminares de la propuesta que confirman la viabilidad de la propuesta.

  9. In situ fluorescence spectroscopy correlates ionomer degradation to reactive oxygen species generation in an operating fuel cell.

    Science.gov (United States)

    Prabhakaran, Venkateshkumar; Arges, Christopher G; Ramani, Vijay

    2013-11-21

    The rate of generation of reactive oxygen species (ROS) within the polymer electrolyte membrane (PEM) of an operating proton exchange member fuel cell (PEMFC) was monitored using in situ fluorescence spectroscopy. A modified barrier layer was introduced between the PEM and the electrocatalyst layer to eliminate metal-dye interactions and fluorescence resonance energy transfer (FRET) effects during measurements. Standard fuel cell operating parameters (temperature, relative humidity, and electrode potential) were systematically varied to evaluate their influence on the rate of ROS generation during PEMFC operation. Independently, the macroscopic rate of PEM degradation was measured by monitoring the fluoride ion emission rate (FER) in the effluent stream at each operating condition. The ROS generation reaction rate constant (estimated from the in situ fluorescence experiments) correlated perfectly with the measured FER across all conditions, demonstrating unequivocally for the first time that a direct correlation exists between in situ ROS generation and PEM macroscopic degradation. The activation energy for ROS generation within the PEM was estimated to be 12.5 kJ mol(-1).

  10. Basic molecular spectroscopy

    CERN Document Server

    Gorry, PA

    1985-01-01

    BASIC Molecular Spectroscopy discusses the utilization of the Beginner's All-purpose Symbolic Instruction Code (BASIC) programming language in molecular spectroscopy. The book is comprised of five chapters that provide an introduction to molecular spectroscopy through programs written in BASIC. The coverage of the text includes rotational spectra, vibrational spectra, and Raman and electronic spectra. The book will be of great use to students who are currently taking a course in molecular spectroscopy.

  11. Results of trial operation of new generation assemblies with improved vibration stability for WWER-440 reactors of V-230 and V-213 plants

    International Nuclear Information System (INIS)

    Vasilchenko, I.; Lushin, V.; Shumeev, A.

    2006-01-01

    The main task in developing a fuel design of new generation for WWER-440 power units (particularly for power units of V-213 type) is to increase the effectiveness of fuel utilization. For this purpose the following design solutions were realized: 1) increase of fuel loading (increase of fuel stack in a fuel rod); 2) optimization of the water-uranium relation (at the cost of some decrease of outside diameter of a fuel rod from 9,1 mm to 9,07 mm and increase of fuel rod pitch in a bundle from 12,2 mm up to 12,3 mm); 3) decrease of harmful absorption of neutrons (due to decrease of hafnium content in zirconium materials from 0,05 % to 0,01 % and decrease of zirconium in transition to thickness of FA casing of ERC assembly - 1,5 mm). The parallel task is to increase vibration stability of fuel assemblies based on the verification and justification of the following technical solutions: 1)improvement of vibration stability due to SG rearrangement along the fuel rod bundle height and increasement of height of the first three grids along the course of coolant flow; 2) decreasement of backlashes in the assembly 'fuel rod - support grid' due to introduction of a new elastic tip of fuel rods; 3) introduction of a stiffening rib under the support grid and attachment of the central tube in the support grid by welding; 4) introduction of special sleeve in the protective grid, which permits to fasten a bundle against radial displacements in its upper part; 5) introduction of slots, located at different height marks of the central tube, permits to exclude distortion and destruction of spacing grids as a result of increase of fuel rod temperature; 6) installation of filters at the inlet. According to design considerations with due regard for statistics of fuel assemblies damage, the filters will be mounted at the working assembly (WA) inlet. In new generation fuel assemblies, the problem of decrease of local flash-up of neutrons in the WA peripheral fuel rods, surrounding the CPS

  12. Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of bromobenzene and its perdeuterated isotopologue: Assignment of the vibrations of the S{sub 0}, S{sub 1}, and D{sub 0}{sup +} states of bromobenzene and the S{sub 0} and D{sub 0}{sup +} states of iodobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Andrejeva, Anna; Tuttle, William D.; Harris, Joe P.; Wright, Timothy G., E-mail: Tim.Wright@nottingham.ac.uk [School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2015-12-28

    We report vibrationally resolved spectra of the S{sub 1}←S{sub 0} transition of bromobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study bromobenzene-h{sub 5} as well as its perdeuterated isotopologue, bromobenzene-d{sub 5}. The form of the vibrational modes between the isotopologues and also between the S{sub 0} and S{sub 1} electronic states is discussed for each species, allowing assignment of the bands to be achieved and the activity between states and isotopologues to be established. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts. Previous work and assignments of the S{sub 1} spectra are discussed. Additionally, the vibrations in the ground state cation, D{sub 0}{sup +}, are considered, since these have also been used by previous workers in assigning the excited neutral state spectra. We also examine the vibrations of iodobenzene in the S{sub 0} and D{sub 0}{sup +} states and comment on the previous assignments of these. In summary, we have been able to assign the corresponding vibrations across the whole monohalobenzene series of molecules, in the S{sub 0}, S{sub 1}, and D{sub 0}{sup +} states, gaining insight into vibrational activity and vibrational couplings.

  13. Ship Vibrations

    DEFF Research Database (Denmark)

    Sørensen, Herman

    1997-01-01

    Methods for calculating natural frequencies for ship hulls and for plates and panels.Evaluation of the risk for inconvenient vibrations on board......Methods for calculating natural frequencies for ship hulls and for plates and panels.Evaluation of the risk for inconvenient vibrations on board...

  14. Vibrational normal modes of diazo-dimedone: A comparative study by Fourier infrared/Raman spectroscopies and conformational analysis by MM/QM

    Science.gov (United States)

    Téllez Soto, C. A.; Ramos, J. M.; Rianelli, R. S.; de Souza, M. C. B. V.; Ferreira, V. F.

    2007-07-01

    The 2-diazo-5,5-dimethyl-cyclohexane-1,3-dione ( 3) was synthesized and the FT-IR/Raman spectra were measured with the purpose of obtain a full assignment of the vibrational modes. Singular aspects concerning the -C dbnd N dbnd N oscillator are discussed in view of two strong bands observed in the region of 2300-2100 cm -1 in both, Infrared and Raman spectra. The density functional theory (DFT) was used to obtain the geometrical structure and for assisting in the vibrational assignment joint to the traditional normal coordinate analysis (NCA). The observed wavenumbers at 2145 (IR), 2144(R) are assigned as the coupled ν(N dbnd N) + ν(C dbnd N) vibrational mode with higher participation of the N dbnd N stretching. A 2188 cm -1 (IR) and at 2186 cm -1 (R) can be assigned as a overtone of one of ν(CC) normal mode or to a combination band of the fundamentals δ(CCH) found at 1169 cm -1 and the δ (CC dbnd N) found at 1017 cm -1 enhanced by Fermi resonance.

  15. Ultrafast Laser-Based Spectroscopy and Sensing: Applications in LIBS, CARS, and THz Spectroscopy

    Science.gov (United States)

    Leahy-Hoppa, Megan R.; Miragliotta, Joseph; Osiander, Robert; Burnett, Jennifer; Dikmelik, Yamac; McEnnis, Caroline; Spicer, James B.

    2010-01-01

    Ultrafast pulsed lasers find application in a range of spectroscopy and sensing techniques including laser induced breakdown spectroscopy (LIBS), coherent Raman spectroscopy, and terahertz (THz) spectroscopy. Whether based on absorption or emission processes, the characteristics of these techniques are heavily influenced by the use of ultrafast pulses in the signal generation process. Depending on the energy of the pulses used, the essential laser interaction process can primarily involve lattice vibrations, molecular rotations, or a combination of excited states produced by laser heating. While some of these techniques are currently confined to sensing at close ranges, others can be implemented for remote spectroscopic sensing owing principally to the laser pulse duration. We present a review of ultrafast laser-based spectroscopy techniques and discuss the use of these techniques to current and potential chemical and environmental sensing applications. PMID:22399883

  16. Ultrafast Laser-Based Spectroscopy and Sensing: Applications in LIBS, CARS, and THz Spectroscopy

    Directory of Open Access Journals (Sweden)

    Megan R. Leahy-Hoppa

    2010-04-01

    Full Text Available Ultrafast pulsed lasers find application in a range of spectroscopy and sensing techniques including laser induced breakdown spectroscopy (LIBS, coherent Raman spectroscopy, and terahertz (THz spectroscopy. Whether based on absorption or emission processes, the characteristics of these techniques are heavily influenced by the use of ultrafast pulses in the signal generation process. Depending on the energy of the pulses used, the essential laser interaction process can primarily involve lattice vibrations, molecular rotations, or a combination of excited states produced by laser heating. While some of these techniques are currently confined to sensing at close ranges, others can be implemented for remote spectroscopic sensing owing principally to the laser pulse duration. We present a review of ultrafast laser-based spectroscopy techniques and discuss the use of these techniques to current and potential chemical and environmental sensing applications.

  17. Second-harmonic generation circular dichroism spectroscopy from tripod-like chiral molecular films

    International Nuclear Information System (INIS)

    Wang Xiao-Ou; Chen Li-An; Chen Li-Xue; Sun Xiu-Dong; Li Jun-Qing; Li Chun-Fei

    2010-01-01

    The second-harmonic generation (SHG) circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated. The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules. Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed. Influence of chiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied. The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics. All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system. The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes

  18. Dense electro-optic frequency comb generated by two-stage modulation for dual-comb spectroscopy.

    Science.gov (United States)

    Wang, Shuai; Fan, Xinyu; Xu, Bingxin; He, Zuyuan

    2017-10-01

    An electro-optic frequency comb enables frequency-agile comb-based spectroscopy without using sophisticated phase-locking electronics. Nevertheless, dense electro-optic frequency combs over broad spans have yet to be developed. In this Letter, we propose a straightforward and efficient method for electro-optic frequency comb generation with a small line spacing and a large span. This method is based on two-stage modulation: generating an 18 GHz line-spacing comb at the first stage and a 250 MHz line-spacing comb at the second stage. After generating an electro-optic frequency comb covering 1500 lines, we set up an easily established mutually coherent hybrid dual-comb interferometer, which combines the generated electro-optic frequency comb and a free-running mode-locked laser. As a proof of concept, this hybrid dual-comb interferometer is used to measure the absorption and dispersion profiles of the molecular transition of H 13 CN with a spectral resolution of 250 MHz.

  19. Direct comparison of phase-sensitive vibrational sum frequency generation with maximum entropy method: case study of water.

    Science.gov (United States)

    de Beer, Alex G F; Samson, Jean-Sebastièn; Hua, Wei; Huang, Zishuai; Chen, Xiangke; Allen, Heather C; Roke, Sylvie

    2011-12-14

    We present a direct comparison of phase sensitive sum-frequency generation experiments with phase reconstruction obtained by the maximum entropy method. We show that both methods lead to the same complex spectrum. Furthermore, we discuss the strengths and weaknesses of each of these methods, analyzing possible sources of experimental and analytical errors. A simulation program for maximum entropy phase reconstruction is available at: http://lbp.epfl.ch/. © 2011 American Institute of Physics

  20. The Concept of Limitation of the Vibration Generated by Rail-Vehicles at Railway Stations and Railway Crossings

    Science.gov (United States)

    Adamczyk, Jan; Targosz, Jan

    2011-03-01

    One of the possibilities of limitation of effects of dynamic influence of the rail-vehicles is the application of the complex objects of vibroinsulation when the mass of the vibroinsulating element is significant, and that is the case of the transporting machines and devices, when the geometric dimensions of the elements of vibroinsulation system are similar to the slab, where the process of modelling of the vibroinsulation mechanism as a discrete system, creates extreme hazards. The article presents the concept of limitation of effects of dynamic influence of the rail-vehicles and tram-vehicles, mainly in the railway tracks located at the railway stations, tram-stops and other engineering structures. The digital model was developed for simulation regarding the propagation of the vibration to the environment. The results of simulation were the basis for development of the vibroinsulation system for the rail-tracks located at the engineering structures such as railway stations, viaducts. The second part of the article presents the approach for controlling of the tension as a function of load of the railway crossing, which was modelled as discrete-continous model. The continuous systems consist of two elements, that is of the support made of elastomer and of the tension members with controlled tension depending on the crossing load. Together with development and more popular application of tension member systems in engineering structures, among others in vibroinsulation systems, it is important to include into calculations and experiments the dynamic loads of the tension member with the mass attached to it. In case of complex objects of vibroinsulation when the mass of the vibroinsulator is significant, and that is the case of the transporting machines and devices, when the geometric dimensions of the elements of vibroinsulation system are similar to the slab, where the process of modelling of the vibroinsulation mechanism as a discrete system, creates extreme

  1. Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

    Science.gov (United States)

    Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

    1994-05-01

    Infrared spectra of mass-selected clusters NO+(H2O)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 H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

  2. Dissimilar Dynamics of Coupled Water Vibrations

    NARCIS (Netherlands)

    Jansen, Thomas L. C.; Cringus, Dan; Pshenichnikov, Maxim S.

    2009-01-01

    Dissimilar dynamics of coupled stretch vibrations of a water molecule are revealed by two-dimensional, IR correlation spectroscopy. These are caused by essentially non-Gaussian fluctuations of the electric field exerted by the environment on the individual OH stretch vibrations. Non-Gaussian

  3. The vibrational structure of (E,E’)-1,4-diphenyl-1,3-butadiene. Linear dichroism FTIR spectroscopy and quantum chemical calculations

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Møller, Søren; Spanget-Larsen, Jens

    2006-01-01

    than 40 vibrational transitions. The observed IR wavenumbers, relative intensities, and polarization directions were generally well reproduced by the results of a harmonic analysis based on B3LYP/cc-pVTZ density functional theory (DFT). The combined experimental and theoretical results led to proposal...... of a nearly complete assignment of the IR active fundamentals of DPB, involving reassignment of a number of transitions. In addition, previously published Raman spectra of DPB were well predicted by the B3LYP/cc-pVTZ calculations....

  4. Novel active vibration absorber with magnetorheological fluid

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, T; Ehrlich, J; Boese, H [Fraunhofer-Institut fuer Silicatforschung ISC, Neunerplatz 2, D-97082 Wuerzburg (Germany)], E-mail: thomas.gerlach@isc.fraunhofer.de

    2009-02-01

    Disturbing vibrations diminish the performance of technical high precision devices significantly. In search of a suitable solution for reducing these vibrations, a novel concept of active vibration reduction was developed which exploits the special properties of magnetorheological fluids. In order to evaluate the concept of such an active vibration absorber (AVA) a demonstrator was designed and manufactured. This demonstrator generates a force which counteracts the motion of the vibrating body. Since the counterforce is generated by a centrifugal exciter, the AVA provides the capability to compensate vibrations even in two dimensions. To control the strength of the force transmitted to the vibrating body, the exciter is based on a tunable MR coupling. The AVA was integrated in an appropriate testing device to investigate its performance. The recorded results show a significant reduction of the vibration amplitudes by an order of magnitude.

  5. Total internal reflection sum-frequency generation spectroscopy and dense gold nanoparticles monolayer: a route for probing adsorbed molecules

    International Nuclear Information System (INIS)

    Tourillon, Gerard; Dreesen, Laurent; Volcke, Cedric; Sartenaer, Yannick; Thiry, Paul A; Peremans, Andre

    2007-01-01

    We show that sum-frequency generation spectroscopy performed in the total internal reflection configuration (TIR-SFG) combined with a dense gold nanoparticles monolayer allows us to study, with an excellent signal to noise ratio and high signal to background ratio, the conformation of adsorbed molecules. Dodecanethiol (DDT) was used as probe molecules in order to assess the potentialities of the approach. An enhancement of more than one order of magnitude of the SFG signals arising from the adsorbed species is observed with the TIR geometry compared to the external reflection one while the SFG non-resonant contribution remains the same for both configurations. Although further work is required to fully understand the origin of the SFG process on nanoparticles, our work opens new possibilities for studying nanostructures

  6. Investigation of the generation of singlet oxygen in ensembles of photoexcited silicon nanocrystals by electron paramagnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Konstantinova, E. A.; Demin, V. A.; Timoshenko, V. Yu.

    2008-01-01

    The generation of singlet oxygen is investigated and its concentration upon photoexcitation of silicon nanocrystals in porous silicon layers is determined using electron paramagnetic resonance spectroscopy. The relaxation times of spin centers, i.e., silicon dangling bonds, in vacuum and in an oxygen atmosphere in the dark and under illumination of the samples are measured for the first time. It is revealed that the spin-lattice relaxation in porous silicon is retarded as compared to that in a single-crystal substrate. From analyzing experimental data, a microscopic model is proposed for interaction of oxygen molecules in the triplet state and spin centers at the surface of silicon nanocrystals. The results obtained have demonstrated that porous silicon holds promise for the use as a photosensitizer of molecular oxygen in biomedical applications

  7. Second harmonic generation spectroscopy in the Reststrahl band of SiC using an infrared free-electron laser

    Energy Technology Data Exchange (ETDEWEB)

    Paarmann, Alexander, E-mail: alexander.paarmann@fhi-berlin.mpg.de; Razdolski, Ilya; Melnikov, Alexey; Gewinner, Sandy; Schöllkopf, Wieland; Wolf, Martin [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)

    2015-08-24

    The Reststrahl spectral region of silicon carbide has recently attracted much attention owing to its potential for mid-infrared nanophotonic applications based on surface phonon polaritons (SPhPs). Studies of optical phonon resonances responsible for surface polariton formation, however, have so far been limited to linear optics. In this Letter, we report the first nonlinear optical investigation of the Reststrahl region of SiC, employing an infrared free-electron laser to perform second harmonic generation (SHG) spectroscopy. We observe two distinct resonance features in the SHG spectra, one attributed to resonant enhancement of the nonlinear susceptibility χ{sup (2)} and the other due to a resonance in the Fresnel transmission. Our work clearly demonstrates high sensitivity of mid-infrared SHG to phonon-driven phenomena and opens a route to studying nonlinear effects in nanophotonic structures based on SPhPs.

  8. Ultrashort Generation Regimes in the All-Fiber Kerr Mode-Locked Erbium-Doped Fiber Ring Laser for Terahertz Pulsed Spectroscopy

    Directory of Open Access Journals (Sweden)

    V. S. Voropaev

    2015-01-01

    Full Text Available Many femtosecond engineering applications require for a stable generation of ultrashort pulses. Thus, in the terahertz pulsed spectroscopy a measurement error in the refractive index is strongly dependent on the pulse duration stability with allowable variation of few femtoseconds. The aim of this work is to study the ultrashort pulses (USP regimes stability in the all – fiber erbium doped ring laser with Kerr mode-locking. The study was conducted at several different values of the total resonator intra-cavity dispersion. Three laser schemes with the intra-cavity dispersion values from -1.232 ps2 to +0.008 ps2 have been studied. In the experiment there were two regimes of generation observed: the stretched pulse generation and ordinary soliton generation. Main attention is focused on the stability of regimes under study. The most stable regime was that of the stretched pulse generation with a spectrum form of sech2 , possible pulse duration of 490 fs at least, repetition rate of 2.9 MHz, and average output power of 17 mW. It is worth noting, that obtained regimes had characteristics suitable for the successful use in the terahertz pulsed spectroscopy. The results may be useful in the following areas of science and technology: a high-precision spectroscopy, optical frequency standards, super-continuum generation, and terahertz pulsed spectroscopy. The future system development is expected to stabilize duration and repetition rate of the obtained regime of ultra-short pulse generation.

  9. Urban vibrations

    DEFF Research Database (Denmark)

    Morrison, Ann; Knudsen, L.; Andersen, Hans Jørgen

    2012-01-01

    In   this   paper   we   describe   a   field   study   conducted   with   a   wearable   vibration   belt   where   we   test   to   determine   the   vibration   intensity   sensitivity   ranges   on   a   large   diverse   group   of   participants   with   evenly   distributed  ages  and...

  10. Catheter based mid-infrared reflectance and reflectance generated absorption spectroscopy

    Science.gov (United States)

    Holman, Hoi-Ying N

    2013-10-29

    A method of characterizing conditions in a tissue, by (a) providing a catheter that has a light source that emits light in selected wavenumbers within the range of mid-IR spectrum; (b) directing the light from the catheter to an area of tissue at a location inside a blood vessel of a subject; (c) collecting light reflected from the location and generating a reflectance spectra; and (d) comparing the reflectance spectra to a reference spectra of normal tissue, whereby a location having an increased number of absorbance peaks at said selected wavenumbers indicates a tissue inside the blood vessel containing a physiological marker for atherosclerosis.

  11. Synthesis, structural and vibrational investigation on 2-phenyl-N-(pyrazin-2-yl)acetamide combining XRD diffraction, FT-IR and NMR spectroscopies with DFT calculations.

    Science.gov (United States)

    Lukose, Jilu; Yohannan Panicker, C; Nayak, Prakash S; Narayana, B; Sarojini, B K; Van Alsenoy, C; Al-Saadi, Abdulaziz A

    2015-01-25

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-phenyl-N-(pyrazin-2-yl)acetamide have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized by using the HF/6-31G(6D,7F) and B3LYP/6-31G(6D,7F) calculations. The geometrical parameters are in agreement with the XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Gauge-including atomic orbital (1)H-NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was performed by the DFT method. First hyperpolarizability is calculated in order to find its role in non linear optics. From the XRD data, in the crystal, molecules are held together by strong C-H⋯O and N-H⋯O intermolecular interactions. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Electron Spin Resonance Spectroscopy for Studying the Generation and Scavenging of Reactive Oxygen Species by Nanomaterials

    Science.gov (United States)

    Yin, Jun-Jie; Zhao, Baozhong; Xia, Qingsu; Fu, Peter P.

    2013-09-01

    One fundamental mechanism widely described for nanotoxicity involves oxidative damage due to generation of free radicals and other reactive oxygen species. Indeed, the ability of nanoscale materials to facilitate the transfer of electrons, and thereby promote oxidative damage or in some instances provide antioxidant protection, may be a fundamental property of these materials. Any assessment of a nanoscale material's safety must therefore consider the potential for toxicity arising from oxidative damage. Therefore, rapid and predictive methods are needed to assess oxidative damage elicited by nanoscale materials. The use of electron spin resonance (ESR) to study free radical related bioactivity of nanomaterials has several advantages for free radical determination and identification. Specifically it can directly assess antioxidant quenching or prooxidant generation of relevant free radicals and reactive oxygen species. In this chapter, we have reported some nonclassical behaviors of the electron spin relaxation properties of unpaired electrons in different fullerenes and the investigation of anti/prooxidant activity by various types of nanomaterials using ESR. In addition, we have reviewed the mechanisms of free radical formation photosensitized by different nanomaterials. This chapter also included the use of spin labels, spin traps and ESR oximetry to systematically examine the enzymatic mimetic activities of nanomaterials.

  13. Optical spectroscopy of vacancy related defects in silicon carbide generated by proton irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kasper, C.; Sperlich, A.; Simin, D.; Astakhov, G.V. [Experimental Physics VI, Julius Maximilian University of Wuerzburg (Germany); Kraus, H. [Japan Atomic EnergyAgency, Takasaki, Gunma (Japan); Experimental Physics VI, Julius Maximilian University of Wuerzburg (Germany); Makino, T.; Sato, S.I.; Ohshima, T. [Japan Atomic EnergyAgency, Takasaki, Gunma (Japan); Dyakonov, V. [Experimental Physics VI, Julius Maximilian University of Wuerzburg (Germany); ZAE Bayern, Wuerzburg (Germany)

    2016-07-01

    Defects in silicon carbide (SiC) received growing attention in recent years, because they are promising candidates for spin based quantum information processing. In this study we examine silicon vacancies in 4H-SiC crystals generated by proton irradiation. By the use of confocal microscopy the implantation depth of Si vacancies for varying proton energies can be verified. An important issue is to ascertain the nature and distribution of the defects. For this purpose, we use the characteristic photoluminescence spectrum of Si vacancies, whose intensity is proportional to the defect density. Using xyz-scans, where the photoluminescence at each mapping point is recorded, one can thus determine the vacancies nature and their distribution in the SiC crystal. Additionally we verify the nature of the examined defects by measuring their uniquely defined zero-field-splitting by using ODMR associated with defect spins.

  14. 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

  15. Characterization of an Atmospheric-Pressure Argon Plasma Generated by 915 MHz Microwaves Using Optical Emission Spectroscopy

    Directory of Open Access Journals (Sweden)

    Robert Miotk

    2017-01-01

    Full Text Available The paper presents the investigations of an atmospheric-pressure argon plasma generated at 915 MHz microwaves using the optical emission spectroscopy (OES. The 915 MHz microwave plasma was inducted and sustained in a waveguide-supplied coaxial-line-based nozzleless microwave plasma source. The aim of presented investigations was to estimate parameters of the generated plasma, that is, excitation temperature of electrons Texc, temperature of plasma gas Tg, and concentration of electrons ne. Assuming that excited levels of argon atoms are in local thermodynamic equilibrium, Boltzmann method allowed in determining the Texc temperature in the range of 8100–11000 K. The temperature of plasma gas Tg was estimated by comparing the simulated spectra of the OH radical to the measured one in LIFBASE program. The obtained Tg temperature ranged in 1200–2800 K. Using a method based on Stark broadening of the Hβ line, the concentration of electrons ne was determined in the range from 1.4 × 1015 to 1.7 × 1015 cm−3, depending on the power absorbed by the microwave plasma.

  16. Next-Generation Microshutter Arrays for Large-Format Imaging and Spectroscopy

    Science.gov (United States)

    Moseley, Samuel; Kutyrev, Alexander; Brown, Ari; Li, Mary

    2012-01-01

    A next-generation microshutter array, LArge Microshutter Array (LAMA), was developed as a multi-object field selector. LAMA consists of small-scaled microshutter arrays that can be combined to form large-scale microshutter array mosaics. Microshutter actuation is accomplished via electrostatic attraction between the shutter and a counter electrode, and 2D addressing can be accomplished by applying an electrostatic potential between a row of shutters and a column, orthogonal to the row, of counter electrodes. Microelectromechanical system (MEMS) technology is used to fabricate the microshutter arrays. The main feature of the microshutter device is to use a set of standard surface micromachining processes for device fabrication. Electrostatic actuation is used to eliminate the need for macromechanical magnet actuating components. A simplified electrostatic actuation with no macro components (e.g. moving magnets) required for actuation and latching of the shutters will make the microshutter arrays robust and less prone to mechanical failure. Smaller-size individual arrays will help to increase the yield and thus reduce the cost and improve robustness of the fabrication process. Reducing the size of the individual shutter array to about one square inch and building the large-scale mosaics by tiling these smaller-size arrays would further help to reduce the cost of the device due to the higher yield of smaller devices. The LAMA development is based on prior experience acquired while developing microshutter arrays for the James Webb Space Telescope (JWST), but it will have different features. The LAMA modular design permits large-format mosaicking to cover a field of view at least 50 times larger than JWST MSA. The LAMA electrostatic, instead of magnetic, actuation enables operation cycles at least 100 times faster and a mass significantly smaller compared to JWST MSA. Also, standard surface micromachining technology will simplify the fabrication process, increasing

  17. Mid-infrared upconversion spectroscopy

    DEFF Research Database (Denmark)

    Tidemand-Lichtenberg, Peter; Dam, Jeppe Seidelin; Andersen, H. V.

    2016-01-01

    Mid-infrared (MIR) spectroscopy is emerging as an attractive alternative to near-infrared or visible spectroscopy. MIR spectroscopy offers a unique possibility to probe the fundamental absorption bands of a large number of gases as well as the vibrational spectra of complex molecules. In this paper...

  18. In-Situ Measurement of Chirality of Molecules and Molecular Assemblies with Surface Nonlinear Spectroscopy

    International Nuclear Information System (INIS)

    Wang, Hongfei

    2012-01-01

    Developments in quantitative measurement and analysis in nonlinear surface spectroscopy, namely, second harmonic generation linear dichroism (SHG-LD) and sum frequency generation vibrational spectroscopy linear dichroism (SFG-VS-LD), provide new opportunities for probing the surface chirality of monolayers and thin films. In this book chapter, the up-to-date theoretical background and experimental methodology, as well as examples and future perspectives on the developments with surface nonlinear spectroscopy in surface chirality studies are to be summarized and outlined for general readers.

  19. 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.

  20. Molecular Structures, Vibrational Spectroscopy, and Normal-Mode Analysis of M(2)(C&tbd1;CR)(4)(PMe(3))(4) Dimetallatetraynes. Observation of Strongly Mixed Metal-Metal and Metal-Ligand Vibrational Modes.

    Science.gov (United States)

    John, Kevin D.; Miskowski, Vincent M.; Vance, Michael A.; Dallinger, Richard F.; Wang, Louis C.; Geib, Steven J.; Hopkins, Michael D.

    1998-12-28

    The nature of the skeletal vibrational modes of complexes of the type M(2)(C&tbd1;CR)(4)(PMe(3))(4) (M = Mo, W; R = H, Me, Bu(t)(), SiMe(3)) has been deduced. Metrical data from X-ray crystallographic studies of Mo(2)(C&tbd1;CR)(4)(PMe(3))(4) (R = Me, Bu(t)(), SiMe(3)) and W(2)(C&tbd1;CMe)(4)(PMe(3))(4) reveal that the core bond distances and angles are within normal ranges and do not differ in a statistically significant way as a function of the alkynyl substituent, indicating that their associated force constants should be similarly invariant among these compounds. The crystal structures of Mo(2)(C&tbd1;CSiMe(3))(4)(PMe(3))(4) and Mo(2)(C&tbd1;CBu(t)())(4)(PMe(3))(4) are complicated by 3-fold disorder of the Mo(2) unit within apparently ordered ligand arrays. Resonance-Raman spectra ((1)(delta-->delta) excitation, THF solution) of Mo(2)(C&tbd1;CSiMe(3))(4)(PMe(3))(4) and its isotopomers (PMe(3)-d(9), C&tbd1;CSiMe(3)-d(9), (13)C&tbd1;(13)CSiMe(3)) exhibit resonance-enhanced bands due to a(1)-symmetry fundamentals (nu(a) = 362, nu(b) = 397, nu(c) = 254 cm(-)(1) for the natural-abundance complex) and their overtones and combinations. The frequencies and relative intensities of the fundamentals are highly sensitive to isotopic substitution of the C&tbd1;CSiMe(3) ligands, but are insensitive to deuteration of the PMe(3) ligands. Nonresonance-Raman spectra (FT-Raman, 1064 nm excitation, crystalline samples) for the Mo(2)(C&tbd1;CSiMe(3))(4)(PMe(3))(4) compounds and for Mo(2)(C&tbd1;CR)(4)(PMe(3))(4) (R = H, D, Me, Bu(t)(), SiMe(3)) and W(2)(C&tbd1;CMe)(4)(PMe(3))(4) exhibit nu(a), nu(b), and nu(c) and numerous bands due to alkynyl- and phosphine-localized modes, the latter of which are assigned by comparisons to FT-Raman spectra of Mo(2)X(4)L(4) (X = Cl, Br, I; L = PMe(3), PMe(3)-d(9))(4) and Mo(2)Cl(4)(AsMe(3))(4). Valence force-field normal-coordinate calculations on the model compound Mo(2)(C&tbd1;CH)(4)P(4), using core force constants transferred from a calculation