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Sample records for fluorescence spectra vibrational

  1. Vibration and Fluorescence Spectra of Porphyrin- CoredBis(methylol-propionic Acid Dendrimers

    Directory of Open Access Journals (Sweden)

    Boris Minaev

    2009-03-01

    Full Text Available Bis-MPA dendron-coated free-base tetraphenylporphyrin and zinc-tetraphenyl-porphyrin (TPPH2 and TPPZn were studied in comparison with simple porphyrins (H2P, ZnP by theoretical simulation of their infrared, Raman and electronic absorption spectra, as well as fluorescense emission. Infrared and fluorescence spectra of the dendrimers were measured and interpreted along with time-resolved measurements of the fluorescence. The 0-1 emission band of the dendron substituted TPPZn was found to experience a "heavy substitution"-effect. The 0-1 vibronic emission signal is associated with a longer decay time (approx. 7 - 8 ns than the 0-0 emission (approx. 1 - 1.5 ns. The former contributed with more relative emission yield for larger dendron substituents, in agreement with the appearance of steady-state emission spectra showing increased contribution from the 0-1 vibronic fluorescence band at 650 nm. No such substitution effect was observed in the electronic or vibrational spectra of the substituted free-base variant, TPPH2. Vibration spectra of the parent porphyrins (H2P, ZnP, TPPH2 and TPPZn were calculated by density functional theory (DFT using the B3LYP/6-31G** approximation and a detailed analysis of the most active vibration modes was made based on both literature and our own experimental data. Based on the results of theoretical calculations the wide vibronic bands in the visible region were assigned. The vibronic structure also gave a qualitative interpretation of bands in the electronic absorption spectra as well as in fluorescence emission depending on the size of dendrimer substitution. From the results of time-dependent DFT calculations it is suggested that the TPPZn-cored dendrimers indicate strong vibronic interaction and increased Jahn-Teller distortion of the prophyrin core for larger dendrimer generations. Specifically, this leads to the entirely different behaviour of the emission spectra upon substitution of the TPPH2 and TPPZn

  2. Vibrational spectra study of fluorescent dendrimers built from the cyclotriphosphazene core with terminal dansyl and carbamate groups

    Science.gov (United States)

    Furer, V. L.; Vandyukova, I. I.; Vandyukov, A. E.; Fuchs, S.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2011-08-01

    The FTIR and FT Raman spectra of the "Janus"-type dendrimers, possessing five carbamate groups on one side and five fluorescent dansyl derivatives on the other side, with amide G1 and hydrazone G2 central linkages were studied. These surface-block dendrimers are obtained by the coupling of two different dendrons. The FTIR and FT-Raman spectra of the zero generation dendrons, built from the hexafunctional cyclotriphosphazene core, with five dansyl terminal groups and one carbamate G0 v and one oxybenzaldehyde function G0v have been recorded. The structural optimization and normal mode analysis were performed for dendron G0v on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendron molecule G0v has a concave lens structure with planar -O-C6H4-CHdbnd O fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendron G0v were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1597 cm -1 show marked changes of the optical density in dependence of substituents in the aromatic ring. The frequencies of ν(N-H) bands in the IR spectra reveal the presence of the different types of H-bonds in the dendrimers.

  3. Vibrational spectra of aminoacetonitrile

    International Nuclear Information System (INIS)

    Bak, B.; Hansen, E.L.; Nicolaisen, F.M.; Nielsen, O.F.

    1975-01-01

    The preparation of pure, stable aminoacetonitrile(1-amino, 1'-cyanomethane)CH 2 NH 2 CN (1) is described. The Raman spectrum, now complete, and a novel infrared spectrum extending over the 50-3600 cm -1 region are reported. A tentative normal vibration analysis is presented and supported by Raman and infrared data from the spectra of CH 2 NHDCN (2) and CH 2 ND 2 CN (3). The predominance of the trans rotamer may be attributed to intramolecular hydrogen bonding but this is too unimportant to influence the vibrational frequencies of gaseous 1, 2, and 3. However, large gas/liquid frequency shifts occur. (author)

  4. Lattice vibration spectra. 16

    International Nuclear Information System (INIS)

    Lutz, H.D.; Willich, P.

    1977-01-01

    The FIR absorption spectra of pyrite type compounds RuS 2 , RuSsub(2-x)Sesub(x), RuSe 2 , RuTe 2 , OsS 2 , OsSe 2 , and PtP 2 as well as loellingite type phosphides FeP 2 , RuP 2 , and OsP 2 are reported. For RuS 2 , RuSe 2 , RuTe 2 , OsS 2 , and PtP 2 all of the five infrared allowed modes (k = 0) are observed. As a first result of a numerical normal coordinate treatment vibration forms of pyrite structure are communicated. The spectra show that lattice forces of corresponding sulfides, tellurides, and phosphides are about the same strength, but increase strongly by substitution of iron by ruthenium and especially of ruthenium by osmium. The lattice constants of the RuSsub(2-x)Sesub(x) solid solution obey Vegard's rule. (author)

  5. Vibrational spectra of ordered perovskites

    NARCIS (Netherlands)

    Corsmit, A.F.; Hoefdraad, H.E.; Blasse, G.

    1972-01-01

    The vibrational spectra of the molecular M6+O6 (M = Mo, Te, W) group in ordered perovskites of the type Ba2M2+M6+O6 are reported. These groups have symmetry Oh, whereas their site symmetry is also Oh. An assignment of the internal vibrations is presented.

  6. [Micro-Raman and fluorescence spectra of several agrochemicals].

    Science.gov (United States)

    Xiao, Yi-lin; Zhang, Peng-xiang; Qian, Xiao-fan

    2004-05-01

    Raman and fluorescence spectra from several agrochemicals were measured, which are sold for the use in vegetables, fruits and grains. Characteristic vibration Raman peaks from some of the agrochemicals were recorded, hence the spectra can be used for their identification. Other marketed agrochemicals demonstrated strong fluorescence under 514.5 nm excitation. It was found that the fluorescence spectra of the agrochemicals are very different. According to these results one can detect the trace amount of agrochemicals left on the surface of fruits, vegetables and grains in situ and conveniently.

  7. Franck-Condon fingerprinting of vibration-tunneling spectra.

    Science.gov (United States)

    Berrios, Eduardo; Sundaradevan, Praveen; Gruebele, Martin

    2013-08-15

    We introduce Franck-Condon fingerprinting as a method for assigning complex vibration-tunneling spectra. The B̃ state of thiophosgene (SCCl2) serves as our prototype. Despite several attempts, assignment of its excitation spectrum has proved difficult because of near-degenerate vibrational frequencies, Fermi resonance between the C-Cl stretching mode and the Cl-C-Cl bending mode, and large tunneling splittings due to the out-of-plane umbrella mode. Hence, the spectrum has never been fitted to an effective Hamiltonian. Our assignment approach replaces precise frequency information with intensity information, eliminating the need for double resonance spectroscopy or combination differences, neither of which have yielded a full assignment thus far. The dispersed fluorescence spectrum of each unknown vibration-tunneling state images its character onto known vibrational progressions in the ground state. By using this Franck-Condon fingerprint, we were able to determine the predominant character of several vibration-tunneling states and assign them; in other cases, the fingerprinting revealed that the states are strongly mixed and cannot be characterized with a simple normal mode assignment. The assigned transitions from vibration-tunneling wave functions that were not too strongly mixed could be fitted within measurement uncertainty by an effective vibration-tunneling Hamiltonian. A fit of all observed vibration-tunneling states will require a full resonance-tunneling Hamiltonian.

  8. Vibrational spectra for hydrogenated amorphous semiconductors

    International Nuclear Information System (INIS)

    Kamitakahara, W.A.; Bouchard, A.M.; Biswas, R.; Gompf, F.; Suck, J.B.

    1990-01-01

    Hydrogen vibration spectra have been measured by neutron scattering for several amorphous semiconductor materials, including a-Ge:H and a-SiC:H samples containing about 10 at. % H. The data for a-Ge:H are compared in detail with the results of realistic computer simulations

  9. Synthesis and Fluorescence Spectra of Triazolylcoumarin Fluorescent Dyes

    Institute of Scientific and Technical Information of China (English)

    PENG Xian-fu; LI Hong-qi

    2009-01-01

    Much attention is devoted to fluorescent dyes especially those with potential in versatile applications. Reactions under "click" conditions between nonfluorescent 3 - azidocoumarins and terminal alkynes produced 3 -(1, 2, 3- triazol- 1 - yl)cournarins, a novel type of fluorescent dyes with intense fluorescence. The structures of the new coumarins were characterized by 1H NMR, MS, and IR spectra. Fluorescence spectra measurement demonstrated excellent fluorescence performance of the triazolylcoumarins and this click reaction is a promising candidate for bioconjugation and bioimaging applications since both azide and alkynes are quite inert to biological systems.

  10. Vibration spectra of single atomic nanocontacts

    International Nuclear Information System (INIS)

    Bourahla, B; Khater, A; Rafil, O; Tigrine, R

    2006-01-01

    This paper introduces a simple model for an atomic nanocontact, where its mechanical properties are analysed by calculating numerically the local spectral properties at the contact atom and the nearby atoms. The standard methodology for calculating phonon spectral densities is extended to enable the calculation of localized contact modes and local density of states (DOS). The model system considered for the nanocontact consists of two sets of triple parallel semi-infinite atomic chains joined by a single atom in between. The matching method is used, in the harmonic approximation, to calculate the local Green's functions for the irreducible set of sites that constitute the inhomogeneous nanocontact domain. The Green's functions yield the vibration spectra and the DOS for the atomic sites. These are numerically calculated for different cases of elastic hardening and softening of the nanocontact domain. The purpose is to investigate how the local dynamics respond to local changes in the elastic environment. The analysis of the spectra and of the DOS identifies characteristic features and demonstrates the central role of a core subset of these sites for the dynamics of the nanocontact. The system models a situation which may be appropriate for contact atomic force microscopy

  11. Vibrational spectra of double oxides of calcium and indium

    International Nuclear Information System (INIS)

    Porotnikov, N.V.; Kondratov, O.I.; Petrov, K.I.; Olikov, I.I.

    1980-01-01

    Vibrational spectra of Ca 40 In 2 O 4 and Ca 44 In 2 O 4 dioxides have been studied. Calculations of a theoretical vibrational spectrum of isotope-substituted compounds have been carried out in the approximation of polymer chains of the valence-force field method. The assignment of experimental spectra is proposed. The force field of crystals is evaluated [ru

  12. [Fluorescence spectra analysis of the scrophularia soup].

    Science.gov (United States)

    Yan, Li-hua; Song, Feng; Han, Juan; Su, Jing; Qu, Fei-fei; Song, Yi-zhan; Hu, Bo-lin; Tian, Jian-guo

    2008-08-01

    The cold-water and boiled-water soaked scrophularia soups have been prepared. The emission and excitation spectra of each scrophularia soup under different conditions have been measured at room temperature. The pH values of the different scrophularia soups have been also detected. There are obvious differences between the cold-water soaked scrophularia soup and the boiled-water soaked scrophularia. For both soups the emission wavelength increases with the wavelength of the excitation, but the peaks of the emission spectra for cold-water and boiled-water soaked scrophularia soup are different, which are 441 and 532 nm, respectively. Excitation spectrum has double peaks in the cold-water soaked scrophularia soup while only one peak with longer wavelength in the boiled-water soaked one. The pH value changes from 5.5 to 4.1. According to the organic admixture fluorescence mechanism we analyzed the reasons of the experimental results. Through heating, the interaction in different fluorescence molecular and the energy transfer process in the same fluorescence molecular become more active, and the conjugate structures and the generation of hydrogen bonds, increase. The fluorescence measurement is of value for the scrophularia pharmacology analysis and provides an analytical method for the quality identification of scrophularia soup.

  13. Molecular vibrations the theory of infrared and Raman vibrational spectra

    CERN Document Server

    Wilson, E Bright; Cross, Paul C

    1980-01-01

    Pedagogical classic and essential reference focuses on mathematics of detailed vibrational analyses of polyatomic molecules, advancing from application of wave mechanics to potential functions and methods of solving secular determinant.

  14. Vibrational spectra of double oxides of calcium and scandium

    International Nuclear Information System (INIS)

    Porotnikov, N.V.; Kondratov, O.I.; Petrov, K.I.; Olikov, I.I.

    1981-01-01

    The vibrational spectra of calcium and scandium double oxides 40 CaSc 2 O 4 and 44 CaSc 2 O 4 in the range of 30-1000 cm -1 are studied. In the approximation of the polymer chains of the method of valent-force field the calculation of the theoretical vibrational spectrum of isotope-substituted compounds is made, the attribution of the experimental spectra is suggested, the frequency branches of the vibrations of periodic chains are built, the force field of crystals is evaluated [ru

  15. Vibrational spectra and thermodynamics of biomolecule: 5-chlorocytosine

    Czech Academy of Sciences Publication Activity Database

    Rastori, V. K.; Palafox, M. A.; Lang, Kamil; Singhal, S.K.; Soni, R.K.; Sharma, R.

    2006-01-01

    Roč. 44, č. 9 (2006), s. 653-660 ISSN 0019-5596 Institutional research plan: CEZ:AV0Z40320502 Keywords : vibrational spectra * 5-chlorocytosine * laser Raman spectra Subject RIV: CA - Inorganic Chemistry Impact factor: 0.380, year: 2006

  16. Theoretical Interpretation of the Fluorescence Spectra of Toluene and P- Cresol

    Science.gov (United States)

    1994-07-01

    NUMBER OF PAGES Toluene Geometrica 25 p-Cresol Fluorescence Is. PRICE CODE Spectra 17. SECURITY CLASSIFICATION 13. SECURITY CLASSIFICATION 19...State Frequencies of Toluene ................ 19 6 Computed and exp" Ground State Frequencies of p-Cresol ............... 20 7 Correction Factors for...Computed Ground State Vibrational Frequencies ....... 21 8 Computed and Corrected Excited State Frequencies of Toluene ............. 22 9 Computed and

  17. Laser-induced fluorescence spectra of Ba+*-He exciplexes produced in cold He gas

    International Nuclear Information System (INIS)

    Fukuyama, Yoshimitsu; Matsuo, Yukari; Moriwaki, Yoshiki

    2004-01-01

    We report the observation of laser-induced fluorescence spectra of Ba +* -He exciplexes. The experiment is carried out in an environment of cold gaseous helium at a temperature range of 3-30 K. We have observed the emission spectra of exciplexes by means of excitation of the 6p 2 P 32 2 S 12 transition of Ba + ions. It is found that these spectra are redshifted from the D2 emission line in the free space and are composed of several peaks. The experimental results are reproduced well by theoretical calculation of the emission spectra for vibrational levels of Ba +* -He. We also investigate the vibrational dynamics of the 6p 2 Π 32 state of Ba + *-He, and we have determined the collision-induced vibrational relaxation cross sections of the 6p 2 Π 32 state to be 9.7±1.1 A 2 at 15 K

  18. Electronic and vibrational circular dichroism spectra of (R)-(-)-apomorphine

    Energy Technology Data Exchange (ETDEWEB)

    Abbate, Sergio, E-mail: abbate@med.unibs.it [Dipartimento di Scienze Biomediche e Biotecnologie, Universita di Brescia, Viale Europa 11, 25123 Brescia (Italy); CNISM, Consorzio Interuniversitario Scienze Fisiche della Materia, Via della Vasca Navale 84, 00146 Roma (Italy); Longhi, Giovanna; Lebon, France [Dipartimento di Scienze Biomediche e Biotecnologie, Universita di Brescia, Viale Europa 11, 25123 Brescia (Italy); CNISM, Consorzio Interuniversitario Scienze Fisiche della Materia, Via della Vasca Navale 84, 00146 Roma (Italy); Tommasini, Matteo [Dipartimento di Chimica, Materiali e Ingegneria Chimica ' G. Natta' , Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM), Unita di Ricerca del Politecnico di Milano (Dip. CMIC), Piazza Leonardo da Vinci 32, 20133 Milano (Italy)

    2012-09-11

    Highlights: Black-Right-Pointing-Pointer ECD and VCD Spectra of (R)-(-)-apomorphine measured in various solvents. Black-Right-Pointing-Pointer DFT calculations allow to study the protonation state and conformations. Black-Right-Pointing-Pointer Contributions from catechol OH vibrations to the VCD spectra is studied. -- Abstract: Apomorphine is a chiral drug molecule; notwithstanding its extraordinary importance, little attention has been paid to the characterization of its chiroptical properties. Here we report on its electronic circular dichroism (ECD) spectra, recorded in methanol and water, and vibrational circular dichroism (VCD) in methanol and dimethyl sulfoxide (DMSO) solutions. Density functional theory (DFT) calculations have allowed us to interpret the spectra and to evaluate the role of possible conformations, charge-states and interactions with counter ions.

  19. Fluorescent vibration-rotation excitation of cometary C2

    International Nuclear Information System (INIS)

    Gredel, R.; Van Dishoeck, E.F.; Black, J.H.

    1989-01-01

    The statistical equilibrium equations that determine the population densities of the energy levels in cometary C2 molecules due to fluorescent excitation are examined in detail. The adopted model and molecular parameters are discussed, and a theoretical estimate is made of the two intercombination transition moments. From the theoretical population densities in the various rotational levels, flux ratios and synthetic emission profiles are calculated as functions of the a 3Pi(u) - X 1Sigma(g)+ and the c 3Sigma(u)+ - X 3Sigma(g)+ intercombination transition moments. The influence of each of these two transitions separately on the vibrational and rotational excitation temperatures is investigated. The observed emission spectra of the (0,0) Swan band in Comet Halley are presented and compared to the synthetic profiles. 70 references

  20. Fluorescent vibration-rotation excitation of cometary C2

    Science.gov (United States)

    Gredel, Roland; Van Dishoeck, Ewine F.; Black, John H.

    1989-01-01

    The statistical equilibrium equations that determine the population densities of the energy levels in cometary C2 molecules due to fluorescent excitation are examined in detail. The adopted model and molecular parameters are discussed, and a theoretical estimate is made of the two intercombination transition moments. From the theoretical population densities in the various rotational levels, flux ratios and synthetic emission profiles are calculated as functions of the a 3Pi(u) - X 1Sigma(g)+ and the c 3Sigma(u)+ - X 3Sigma(g)+ intercombination transition moments. The influence of each of these two transitions separately on the vibrational and rotational excitation temperatures is investigated. The observed emission spectra of the (0,0) Swan band in Comet Halley are presented and compared to the synthetic profiles.

  1. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  2. CO 2 laser photoacoustic spectra and vibrational modes of heroin ...

    Indian Academy of Sciences (India)

    Heroin, morphine and narcotine are very large molecules having 50, 40 and 53 atoms respectively. Moderately high resolution photoacoustic (PA) spectra have been recorded in 9.6 m and 10.6 m regions of CO2 laser. It is very difficult to assign the modes of vibrations for PA bands by comparison with conventional low ...

  3. The Vibrational Spectra of the Boron Halides and their Molecular ...

    African Journals Online (AJOL)

    The structures, interaction energies and vibrational spectra of the van derWaals complexes formed between boron trifluoride, as Lewis acid, and water and hydrogen sulphide, as Lewis bases, have been determined by means of ab initio calculations at the second-order level of Møller-Plesset perturbation theory, using a ...

  4. Calculation of ground vibration spectra from heavy military vehicles

    Science.gov (United States)

    Krylov, V. V.; Pickup, S.; McNuff, J.

    2010-07-01

    The demand for reliable autonomous systems capable to detect and identify heavy military vehicles becomes an important issue for UN peacekeeping forces in the current delicate political climate. A promising method of detection and identification is the one using the information extracted from ground vibration spectra generated by heavy military vehicles, often termed as their seismic signatures. This paper presents the results of the theoretical investigation of ground vibration spectra generated by heavy military vehicles, such as tanks and armed personnel carriers. A simple quarter car model is considered to identify the resulting dynamic forces applied from a vehicle to the ground. Then the obtained analytical expressions for vehicle dynamic forces are used for calculations of generated ground vibrations, predominantly Rayleigh surface waves, using Green's function method. A comparison of the obtained theoretical results with the published experimental data shows that analytical techniques based on the simplified quarter car vehicle model are capable of producing ground vibration spectra of heavy military vehicles that reproduce basic properties of experimental spectra.

  5. Density functional theory study of vibrational spectra, and ...

    Indian Academy of Sciences (India)

    The FTIR and FT Raman spectra of dacarbazine were recorded in the regions 4000-400 and 3500-100 cm-1, respectively. The optimized geometry, wavenumber, polarizability and several thermodynamic properties of dacarbazine were studied using ab initio Hartree-Fock, MP2 and DFT methods. A complete vibrational ...

  6. Vibrational and electronic spectra of 2-nitrobenzanthrone: An experimental and computational study

    Science.gov (United States)

    Onchoke, Kefa K.; Chaudhry, Saad N.; Ojeda, Jorge J.

    2016-01-01

    The environmental pollutant 2-nitrobenzanthrone (2-NBA) poses human health hazards, and is formed by atmospheric reactions of NOX gases with atmospheric particulates. Though its mutagenic effects have been studied in biological systems, its comprehensive spectroscopic experimental data are scarce. Thus, vibrational and optical spectroscopic analysis (UV-Vis, and fluorescence) of 2-NBA was studied using both experimental and density functional theory employing B3LYP method with 6-311 + G(d,p) basis set. The scaled theoretical vibrational frequencies show good agreement to experiment to within 5 cm- 1 and NBA, respectively. On the basis of normal coordinate analysis complete assignments of harmonic experimental infrared and Raman bands are made. The influence of the nitro group substitution upon the benzanthrone structure and symmetric CH vibrations, and electronic spectra is noted. This study is useful for the development of spectroscopy-mutagenicity relationships in nitrated polycyclic aromatic hydrocarbons.

  7. Quantum algebraic description of vibrational and transitional nuclear spectra

    International Nuclear Information System (INIS)

    Raychev, P.P.; Roussev, R.P.; Inrne, D.

    1995-01-01

    A physically motivated extension of the SU q (2) model of rotational nuclear spectra is introduced, which is applicable in the vibrational and transitional regions as well. The deformation parameter is related to the centrifugal stretching effect, while the new parameter c allows the spectrum to be an expansion in terms of J(J+c) instead of J(J+1), thus describing nuclear anharmonicities in a way similar to the Interacting Boson Model and the Generalized Variable Moment of Inertia model

  8. Dual fluorescence excitation spectra of methyl salicylate in a free jet

    Science.gov (United States)

    Heimbrook, Lou Ann; Kenny, Jonathan E.; Kohler, Bryan E.; Scott, Gary W.

    1981-11-01

    Separate fluorescence excitation spectra of the blue- and UV-emitting forms of methyl salicylate cooled in a free-jet expansion are reported. This study represents the first observation of the detailed vibrational structure of these transitions. The two excitation spectra have no features in common, and their intensity patterns are very different. Many individual lines are ˜2 cm-1 wide (nearly laser limited), although in the excitation spectrum of the UV emission, spectral congestion persists at high energies despite the high degree of cooling. (AIP)

  9. PGOPHER: A program for simulating rotational, vibrational and electronic spectra

    International Nuclear Information System (INIS)

    Western, Colin M.

    2017-01-01

    The PGOPHER program is a general purpose program for simulating and fitting molecular spectra, particularly the rotational structure. The current version can handle linear molecules, symmetric tops and asymmetric tops and many possible transitions, both allowed and forbidden, including multiphoton and Raman spectra in addition to the common electric dipole absorptions. Many different interactions can be included in the calculation, including those arising from electron and nuclear spin, and external electric and magnetic fields. Multiple states and interactions between them can also be accounted for, limited only by available memory. Fitting of experimental data can be to line positions (in many common formats), intensities or band contours and the parameters determined can be level populations as well as rotational constants. PGOPHER is provided with a powerful and flexible graphical user interface to simplify many of the tasks required in simulating, understanding and fitting molecular spectra, including Fortrat diagrams and energy level plots in addition to overlaying experimental and simulated spectra. The program is open source, and can be compiled with open source tools. This paper provides a formal description of the operation of version 9.1. - Highlights: • Easy-to-use graphical interface for assigning and understanding molecular spectra. • Simulates rotational and vibrational structure of many types of molecular spectra. • Fits molecular properties to line positions or spectral contours. • Handles linear molecules and symmetric and asymmetric tops. • Handles perturbations, nuclear and electron spin, and electric and magnetic fields.

  10. Crystal structure and vibrational spectra of melaminium arsenate

    Science.gov (United States)

    Anbalagan, G.; Marchewka, M. K.; Pawlus, K.; Kanagathara, N.

    2015-01-01

    The crystals of the new melaminium arsenate (MAS) [C3H7N6+ṡH2AsO4-] were obtained by the slow evaporation of an aqueous solution at room temperature. Single crystal X-ray diffraction analysis reveals that the crystal belongs to triclinic system with centro symmetric space group P-1. The crystals are built up from single protonated melaminium residues and single dissociated arsenate H2AsO4- anions. The protonated melaminium ring is almost planar. A combination of ionic and donor-acceptor hydrogen-bond interactions linking together the melaminium and arsenate residues forms a three-dimensional network. Vibrational spectroscopic analysis is reported on the basis of FT-IR and FT-Raman spectra recorded at room temperature. Hydrogen bonded network present in the crystal gives notable vibrational effect. DSC has also been performed for the crystal shows no phase transition in the studied temperature range (113-293 K).

  11. Vibrational spectra of solid solution series with ordered perovskite structure

    NARCIS (Netherlands)

    Blasse, G.

    I.R. and Raman spectra are reported for the following three systems: Ba2CaMo1−xTexO6, Ba2−xSrxMgWO6 and Ba2Ca1−xMgxWO6. In the first series the internal vibrations of the M6+O6 octahedra do not influence each other. The intensity of ν1 (MoO6) is five times that of ν1 (TeO6). In the second system

  12. Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Kolesniková, L.; Alonso, E. R.; Mata, S.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Área de Química-Física, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Unidad Asociada CSIC, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2017-04-01

    We report a detailed spectroscopic investigation of the interstellar aminoacetonitrile, a possible precursor molecule of glycine. Using a combination of Stark and frequency-modulation microwave and millimeter wave spectroscopies, we observed and analyzed the room-temperature rotational spectra of 29 excited states with energies up to 1000 cm{sup −1}. We also observed the {sup 13}C isotopologues in the ground vibrational state in natural abundance (1.1%). The extensive data set of more than 2000 new rotational transitions will support further identifications of aminoacetonitrile in the interstellar medium.

  13. Lifetime-vibrational interference effects in resonantly excited x-ray emission spectra of CO

    Energy Technology Data Exchange (ETDEWEB)

    Skytt, P.; Glans, P.; Gunnelin, K. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    The parity selection rule for resonant X-ray emission as demonstrated for O{sub 2} and N{sub 2} can be seen as an effect of interference between coherently excited degenerate localized core states. One system where the core state degeneracy is not exact but somewhat lifted was previously studied at ALS, namely the resonant X-ray emission of amino-substituted benzene (aniline). It was shown that the X-ray fluorescence spectrum resulting from excitation of the C1s at the site of the {open_quotes}aminocarbon{close_quotes} could be described in a picture separating the excitation and the emission processes, whereas the spectrum corresponding to the quasi-degenerate carbons could not. Thus, in this case it was necessary to take interference effects between the quasi-degenerate intermediate core excited states into account in order to obtain agreement between calculations and experiment. The different vibrational levels of core excited states in molecules have energy splittings which are of the same order of magnitude as the natural lifetime broadening of core excitations in the soft X-ray range. Therefore, lifetime-vibrational interference effects are likely to appear and influence the band shapes in resonant X-ray emission spectra. Lifetime-vibrational interference has been studied in non-resonant X-ray emission, and in Auger spectra. In this report the authors discuss results of selectively excited soft X-ray fluorescence spectra of molecules, where they focus on lifetime-interference effects appearing in the band shapes.

  14. Fluorescence Spectra Studies on the Interaction between Lanthanides and Calmodulin

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The conformation of Calmodulin(CaM) induced by lanthanides has been examined using fluorescence methods.With the addition of lanthanide (Ln3+), the intrinsic fluorescence intensity of CaM without calcium ions (Apo-CaM) first increases and then decreases.Ln3+ causes the decrease of intrinsic fluorescence intensity of calcium saturated CaM (Ca2+4-CaM) only at high concentrations.At low concentrations, Ln3+ results not only in the enhancement of fluorescence intensity of Apo-CaM, but also in a blue shift of the maximum emission wavelengh of dansyl labeled calmodulin(Apo-D-CaM).The molecular mechanism of the interaction between Ln3+ and CaM has been discussed in the light of the fluorescence spectra.

  15. Vibration-rotation band intensities in the IR spectra of polyatomic molecules

    International Nuclear Information System (INIS)

    El'kin, M.D.; Kosterina, E.K.; Berezin

    1995-01-01

    Using the curvilinear vibrational coordinates for a nuclear subsystem, expressions for the effective dipole-moment operators are derived in order to analyze the vibrational-rotational transitions in the IR spectra of polyatomic rigid molecules. The explicit expressions obtained for the intensities of hot bands allow one to estimate the influence of the vibration-rotation interaction within the framework of the adopted molecular-vibration model. The suggested method is shown to be suitable for Raman spectra analysis. 12 refs

  16. Algebraic descriptions of nuclear and molecular rotation-vibration spectra

    International Nuclear Information System (INIS)

    Roosmalen, O.S. van.

    1982-01-01

    The application of algebraic models to the description of rotational and vibrational degrees of freedom of nuclei and molecules are discussed. Simple model Hamiltonians are shown to give good agreement with the energy spectra of diatomic molecules and nuclei. Some formal aspects of path integral methods for many-boson systems are treated. The two representations for the quantum mechanical propagator are compared and appear to be identical in leading order in 1/N (N is the number of bosons). Approximations for both are static and dynamic problems are discussed. Applications of mean field techniques are also treated. A description of tri- and tetra-atomic molecules in terms of a U(4)xU(4) and U(4)xU(4)xU(4) group structure is given. Linear molecules appear to correspond with symmetries of O(4) type. S-matrix elements are calculated to test mean field methods, and the results compared with exact calculations. (Auth.)

  17. Crystal field influence on vibration spectra: anhydrous uranyl chloride and dihydroxodiuranyl chloride tetrahydrate

    International Nuclear Information System (INIS)

    Perrin, Andre; Caillet, Paul

    1976-01-01

    Vibrational spectra of anhydrous uranyl chloride UO 2 Cl 2 and so called basic uranyl chloride: dihydroxodiuranyl chloride tetrahydrate /UO 2 (OH) 2 UO 2 /Cl 2 (H 2 O) 4 are reported. Factor group method analysis leads for the first time to complete and comprehensive interpretation of their spectra. Two extreme examples of crystal field influence on vibrational spectra are pointed out: for UO 2 Cl 2 , one is unable to explain spectra without taking into account all the elements of primitive crystalline cell, whilst for dihydroxodiuranyl dichloride tetrahydrate the crystal packing has very little effect on vibrational spectra [fr

  18. Effect of deuteration on the vibrational spectra of organic molecules

    International Nuclear Information System (INIS)

    Billes, Ferenc; Endredi, Henrietta; Varady, Balazs

    2001-01-01

    The stable isotope substitution of organic compounds deforms their vibrational spectra. The modifications of the spectra appear as band shifts and changes in intensities and shapes of the bands. The magnitude of the effect depends on the ratio of the masses of the new and old isotopes and on the atom active position. According to these mentioned reasons large effects can be observed only if hydrogen atoms are substituted. With the effect of the substitution we dealt already in a former lecture. In this lecture we concentrate on the effect of the change of hydrogen to deuterium. We investigate the changes both experimentally and theoretically. There are two possibilities: - the hydrogen atom is in an active position, its interaction with the environment is strong, either it can dissociate or move on the skeleton of the molecule (tautomerism, resonance) and it can build hydrogen bond, (e.g. it is connected to nitrogen and oxygen atoms); - the hydrogen atom is in an indifferent position in the molecule, its interaction with the environment is weak (e.g. it joins carbon atom). When building the hydrogen bond besides the hydrogen donors also acceptors exist, namely, oxygen and nitrogen atoms having non-bonded electron pairs. When comparing the experimental and theoretical (calculated) effects of this type of isotope changes one must take into account that the calculations refer to the isolated molecule while the experimental spectra characterize the compound. The hydrogen bond is a very strong intermolecular interaction and produces tremendous changes in the infrared spectrum of the molecule in comparison to the imagined theoretical spectrum of the molecule. Some bands disappear, appear, or shift and deform drastically. The H/D change diminishes these effects. Of course, these changes entail the shift of several bands. The Raman spectrum is less sensitive to the large dipole moment changes therefore the deuteration effect is there less dramatic. Deuteration of hydrogen

  19. Tautomerism of 4-hydrazinoquinazolines: vibrational spectra and computational study

    Directory of Open Access Journals (Sweden)

    Tetiana Yu. Sergeieva

    2014-03-01

    Full Text Available The tautomerism of 4-hydrazinoquinazoline and its derivatives was investigated. Geometry and thermodynamic parameters were computed theoretically using Gaussian 03 software. All calculations were performed at the MP2 level of theory using the standard 6-31G(d basis. Energetics and relative stabilities of tautomers were compared and analyzed in a gas phase. The effect of solvents (1,4-dioxane, acetic acid, ethanol and water on the tautomeric equlibria was evaluated using PCM. It was determined that solvents induced slight changes in the relative stability. In all cases 4-hydrazinoquinazoline exists predominantly as the amino form. The variation of dipole moments was studied. The anharmonic vibrational wavenumbers for unsubstituted 4-hydrazinoquinazoline were calculated at MP2/6-31G(d level and compared with experimental data. The modes of IR spectra were assigned. The calculated herein wavenumbers and intensities of amino form are in good agreement with those observed experimentally.      

  20. Vibrational spectra of charge transfer complexes of lead phthalocyanine

    International Nuclear Information System (INIS)

    Oza, A.T.; Patel, S.G.; Patel, R.G.; Prajapati, S.M.; Vaidya, Rajiv

    2005-01-01

    Infrared spectra of six charge transfer complexes of lead phthalocyanine (PbPc), namely, PbPc-I 2 , PbPc-TCNQ, PbPc-DDQ, PbPc-chloranil, PbPc-TCNE and PbPc-TNF, where TCNQ=7,7,8,8-tetracyano-1,4-quinodimethane, DDQ=2,3-dichloro-5,6-dicyano-p-benzoquinone, TCNE=tetracyano-p-ethylene and TNF=2,4,5,7-tetranitro-9-fluorenone have been studied in the range of 400-4000 cm -1 . The analysis of featureless absorption is carried out for studying transition across the Peierls gap of 0.225 eV. The electronic absorption envelopes at 1500, 1100 and 3400 cm -1 are found to have Gaussian shapes and not the degenerate oscillators, as found in purely organic conductors. There is a pairing of two electrons on phthalocyanine ligand as required in Little's model, and consequently, the electronic absorption envelope is a doublet. Electronic absorption envelope is a doublet showing two peaks at 1500 and 1100 cm -1 , indicating a two-electron problem in PbPc. Metal-ligand vibrations between 400 and 700 cm -1 lead to indirect transition between the valence and conduction bands and phonon-mediated coupling between metal chains and the side chains

  1. Fluorescence spectra and collisional energy transfer of YO (A2PIsub(1/2, 3/2)) molecules in flames

    International Nuclear Information System (INIS)

    Wijchers, T.

    1981-01-01

    The aim of this investigation was (a) to determine, from fluorescence spectra in the visible, the normalized, radiatively induced extra populations of vibronic levels of a diatomic metal compound; (b) to calculate therefrom the normalized collisional transition probabilities between vibrational levels in an excited electronic state. Yttrium monoixde (YO) was chosen as the metal compound and A 2 PIsub(1/2,3/2) as the state(s) to be investigated. (Auth.)

  2. Molecular Geometry And Vibrational Spectra of 2'-chloroacetanilide

    International Nuclear Information System (INIS)

    Gokce, H.

    2008-01-01

    The molecular structure, vibrational frequencies and the corresponding vibrational assingments of 2'-chloroacetanilide in the ground state have been calculated by using Hartree-Fock (HF) and Density Functional Theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set. The obtained vibrational frequencies and optimized geometric parameters (bond lenghts and angles) are in very good agreement with the experimental data. The comparison of the observed and calculated vibrational frequencies assignments of 2'-chloroacetanilide exhibit that the scaled DFT/B3LYP method is superior to be scaled HF method. Furthermore the calculated Infrared and Raman intensities are also reported

  3. Green synthesis, structure and fluorescence spectra of new azacyanine dyes

    Science.gov (United States)

    Enchev, Venelin; Gadjev, Nikolai; Angelov, Ivan; Minkovska, Stela; Kurutos, Atanas; Markova, Nadezhda; Deligeorgiev, Todor

    2017-11-01

    A series of symmetric and unsymmetric monomethine azacyanine dyes (monomethine azacyanine and merocyanine sulfobetaines) were synthesized with moderate to high yields via a novel method using microwave irradiation. The compounds are derived from a condensation reaction between 2-thiomethylbenzotiazolium salts and 2-imino-3-methylbenzothiazolines proceeded under microwave irradiation. The synthetic approach involves the use of green solvent and absence of basic reagent. TD-DFT calculations were performed to simulate absorption and fluorescent spectra of synthesized dyes. Absorption maxima, λmax, of the studied dyes were found in the range 364-394 nm. Molar absorbtivities were evaluated in between 40300 and 59200 mol-1 dm3 cm-1. Fluorescence maxima, λfl, were registered around 418-448 nm upon excitation at 350 nm. A slight displacements of theoretically estimated absorption maxima according to experimental ones is observed. The differences are most probably due to the fact that the DFT calculations were carried out without taking into account the solvent effect. In addition, the merocyanine sulfobetaines also fluorescence in blue optical range (420-480 nm) at excitation in red range (630-650 nm).

  4. Fluorescence spectra of benign and malignant prostate tissues

    International Nuclear Information System (INIS)

    AlSalhi, M S; Masilamani, V; Atif, M; Farhat, K; Rabah, D; Al Turki, M R

    2012-01-01

    In this study, fluorescence emission spectrum (FES), Stokes' shift spectrum (SSS), and reflectance spectrum (RS) of benign (N = 12) and malignant prostate tissues (N = 8) were investigated to discriminate the two types of tissues. The FES was done with the excitation at 325 nm only; SSS with Δλ = 70 and Δλ = 0, the latter being equivalent to reflectance spectra. Of the three modes of spectra, SSS with Δλ = 70 nm showed the best discrimination. There were four important bands, one at 280 nm (due to tryptophan); 320 nm (due to elastin and tryptophan); 355 and 385 (due to NADH) and 440 nm (due to flavin). From the relative intensities of these bands, three ratios were evaluated. Similarly another two ratios were obtained from reflectance spectra and one more from FES. Thus, there are 6 ratio parameters which represent the relative concentration of tryptophan, elastin, nicotinamide adenine dinucleotide (NADH), and flavin. A statistical analysis showed that benign and malignant tissues could be classified with accuracy greater than 90%. This report is only for in vitro analysis; but employing optical fiber, this can be extended to in vivo analysis too, so that benign tumor could be distinguished without surgery

  5. Vibrational spectra and crystal lattice dynamics of hexahydrates of zinc potassium and ammonium sulfates

    Science.gov (United States)

    Barashkov, M. V.; Komyak, A. I.; Shashkov, S. N.

    2000-03-01

    The IR spectra and polarized Raman spectra of crystals of hexahydrates of zinc potassium and ammonium sulfates have been obtained experimentally at 93 K and at room temperature. The frequencies and modes of normal vibrations of the octahedral complex [Zn(H2O)6]2+ have been calculated. The assignment of the observed lines of the internal and external vibrations of the crystal cell has been made by calculations and by factor-group analysis.

  6. Vibrational spectra and normal co-ordinate analysis of 2-aminopyridine and 2-amino picoline.

    Science.gov (United States)

    Jose, Sujin P; Mohan, S

    2006-05-01

    The Fourier transform infrared (FT-IR) and Raman (FT-R) spectra of 2-aminopyridine and 2-amino picoline were recorded and the observed frequencies were assigned to various modes of vibration in terms of fundamentals by assuming Cs point group symmetry. A normal co-ordinate analysis was also carried out for the proper assignment of the vibrational frequencies using simple valence force field. A complete vibrational analysis is presented here for the molecules and the results are briefly discussed.

  7. Theoretical Studies Of Molecular Structure And Vibrational Spectra Of 5-Aminolevulinic Acid Hexyl Ester

    International Nuclear Information System (INIS)

    Comert, H.

    2010-01-01

    The molecular geometry and vibrational frequencies of The 5-Aminolevulinic acid's hexyl ester (ALA-H) in the ground state have been calculated using Hartree-Fock (HF) and Density functional method (B3LYP) with 6-31++G(d) basis set. The calculated vibrational spectra and geometric parameters of title compound were compered with experimental ones.

  8. Effect of detector size and position on measured vibration spectra of strings and rods

    International Nuclear Information System (INIS)

    Lipcsei, S.; Kiss, S.; Por, G.

    1993-04-01

    Weight functions of string and rod vibrations are described by standing and travelling wave models. The effects of detector size and position on the measured vibration spectra was investigated, and the main characteristics of the transfer function were calculated by a simple standing wave model. The theoretical results were compared with data from laboratory rod vibration experiments, and with pressure fluctuation spectra obtained at the Paks Nuclear Power Plant. In addition, some fundamental physical consequences can be made using the theory of superposition of travelling waves and their reflection on clamped rod ends. (R.P.) 5 refs.; 10 figs

  9. Nonclassical polarization effects in fluorescence emission spectra from microdroplets

    Science.gov (United States)

    Arnold, S.; Goddard, N. L.; Hill, S. C.

    1999-12-01

    We report a pronounced nonclassical polarization effect on the shape of fluorescence emission spectra from isolated microdroplets containing a dilute solution of soluble fluors or a dilute layer of surfactant fluors. We see different spectral shapes for 90° scattering when comparing between IVV, IVH, IHH, IHV. However, we measure the largest difference in spectral shape in the surfactant case, with the incident polarization directed toward the detector (IHV vs IHH). Imaging reveals that the emission in this case principally arises from two distinct regions near the surface of the droplet, which are diametrically opposed and along the axis of the incident laser beam. The effect appears to be the direct result of coupling between molecular emission moments and electromagnetic modes of the droplet. It is not the molecule which radiates but the molecule microvessel. Directional emission is sensitive to the polarization of the electromagnetic mode which is stimulated by the coupling.

  10. DFT study of structure, IR and Raman spectra of the fluorescent "Janus" dendron built from cyclotriphosphazene core

    Science.gov (United States)

    Furer, V. L.; Vandyukova, I. I.; Vandyukov, A. E.; Fuchs, S.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

    2011-11-01

    The FTIR and FT-Raman spectra of the zero generation dendron, possessing five fluorescent dansyl terminal groups, cyclotriphosphazene core, and one carbamate function G0v were studied. The structural optimization and normal mode analysis were performed for G0v dendron on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendron molecule G0v has a concave lens structure with slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of G0v dendron were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The frequency of ν(N-H) band in the IR spectrum reveal the presence of H-bonds in the G0v dendron.

  11. Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

    International Nuclear Information System (INIS)

    Komyak, A.I.; Umrejko, D.S.; Posledovich, M.R.

    2013-01-01

    Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO 2 2+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm -1 , among which the frequencies at 724 and 1380 cm -1 are doubly degenerate and attributed to E’ symmetry of the point group D 3h . When this group is uranium coordinated, its symmetry level is lowered to C 2v , all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm -1 . (authors)

  12. Fluorescence of Bacteria, Pollens, and Naturally Occurring Airborne Particles: Excitation/Emission Spectra

    National Research Council Canada - National Science Library

    Hill, Steven C; Mayo, Michael W; Chang, Richard K

    2009-01-01

    The fluorescence intensity as a function of excitation and emission wavelengths (EEM spectra) was measured for different species of bacteria, biochemical constituents of cells, pollens, and vegetation...

  13. Vibrational spectra of crystalline formic and acetic acid isotopologues by inelastic neutron scattering and numerical simulations

    International Nuclear Information System (INIS)

    Johnson, M.R.; Trommsdorff, H.P.

    2009-01-01

    Vibrational spectra of crystalline powder of four isotopologues of formic acid (HCOOH, HCOOD, DCOOH, DCOOD) and of acetic acid (CH 3 COOH, CH 3 COOD, CD 3 COOH, CD 3 COOD) were recorded at 20 K by inelastic neutron scattering. These spectra are compared with computed spectra based on harmonic force fields derived from periodic density functional theory (DFT) calculations. The assignment of all internal vibrations is obvious from the spectral changes under isotopic substitution. Discrepancies between calculation and experiment expose the over evaluation of the strength of the hydrogen bond by these standard DFT calculations

  14. Correlating the vibrational spectra of structurally related molecules: A spectroscopic measure of similarity.

    Science.gov (United States)

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

    2018-03-05

    Using catastrophe theory and the concept of a mutation path, an algorithm is developed that leads to the direct correlation of the normal vibrational modes of two structurally related molecules. The mutation path is defined by weighted incremental changes in mass and geometry of the molecules in question, which are successively applied to mutate a molecule into a structurally related molecule and thus continuously converting their normal vibrational spectra from one into the other. Correlation diagrams are generated that accurately relate the normal vibrational modes to each other by utilizing mode-mode overlap criteria and resolving allowed and avoided crossings of vibrational eigenstates. The limitations of normal mode correlation, however, foster the correlation of local vibrational modes, which offer a novel vibrational measure of similarity. It will be shown how this will open new avenues for chemical studies. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  15. A new scaling algorithm for predicting vibrational spectra of ...

    Indian Academy of Sciences (India)

    Administrator

    RMS error 5 cm. –1. 4. Glycine molecule. Glycine exists as a neutral molecule in the gas phase. The vibrational spectrum of glycine in the gas phase has been studied recently by theory and experiment. 12. To check the methodology we tried. MP2/6-311++G** calculations on the most stable conformation of glycine. All the ...

  16. Molecular vibration-rotation spectra starting from the Fues potential

    International Nuclear Information System (INIS)

    Ley Koo, E.

    1976-01-01

    The solution of Schroedinger's equation for the Fues potential is analyzed and compared with the corresponding problems for the Coulomb, harmonic oscillator and molecular potentials. These comparisons allow us to emphasize certain pedagogical, conceptual and computational advantages of the Fues potential which make it a favorable alternative as the starting point in the analysis of molecular vibration-rotation and in the determination of potential energy curves. (author)

  17. 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

  18. Probing symmetry and symmetry breaking in resonant soft-x-ray fluorescence spectra of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Glans, P.; Gunnelin, K.; Guo, J. [Uppsala Univ. (Sweden)] [and others

    1997-04-01

    Conventional non-resonant soft X-ray emission brings about information about electronic structure through its symmetry and polarization selectivity, the character of which is governed by simple dipole rules. For centro-symmetric molecules with the emitting atom at the inversion center these rules lead to selective emission through the required parity change. For the more common classes of molecules which have lower symmetry or for systems with degenerate core orbitals (delocalized over identical sites), it is merely the local symmetry selectivity that provides a probe of the local atomic orbital contribution to the molecular orbital. For instance, in X-ray spectra of first row species the intensities essentially map the p-density at each particular atomic site, and, in a molecular orbital picture, the contribution of the local p-type atomic orbitals in the LCAO description of the molecular orbitals. The situation is different for resonant X-ray fluorescence spectra. Here strict parity and symmetry selectivity gives rise to a strong frequency dependence for all molecules with an element of symmetry. In addition to symmetry selectivity the strong frequency dependence of resonant X-ray emission is caused by the interplay between the shape of a narrow X-ray excitation energy function and the lifetime and vibrational broadenings of the resonantly excited core states. This interplay leads to various observable effects, such as linear dispersion, resonance narrowing and emission line (Stokes) doubling. Also from the point of view of polarization selectivity, the resonantly excited X-ray spectra are much more informative than the corresponding non-resonant spectra. Examples are presented for nitrogen, oxygen, and carbon dioxide molecules.

  19. VIBRATIONAL SPECTRA OF t-BUTYL ALCOHOL, t-BUTYLAMINE ...

    African Journals Online (AJOL)

    a

    good stray light rejection. A Spectra-Physics ... the spectrometer. The vial was then spun to enhance the Raman signal and reduce the risk of .... *Abbreviations used: m, medium; s, strong; v, very; w, weak; sh, shoulder; -, not detected due to the ...

  20. PGOPHER: A program for simulating rotational, vibrational and electronic spectra

    Science.gov (United States)

    Western, Colin M.

    2017-01-01

    The PGOPHER program is a general purpose program for simulating and fitting molecular spectra, particularly the rotational structure. The current version can handle linear molecules, symmetric tops and asymmetric tops and many possible transitions, both allowed and forbidden, including multiphoton and Raman spectra in addition to the common electric dipole absorptions. Many different interactions can be included in the calculation, including those arising from electron and nuclear spin, and external electric and magnetic fields. Multiple states and interactions between them can also be accounted for, limited only by available memory. Fitting of experimental data can be to line positions (in many common formats), intensities or band contours and the parameters determined can be level populations as well as rotational constants. PGOPHER is provided with a powerful and flexible graphical user interface to simplify many of the tasks required in simulating, understanding and fitting molecular spectra, including Fortrat diagrams and energy level plots in addition to overlaying experimental and simulated spectra. The program is open source, and can be compiled with open source tools. This paper provides a formal description of the operation of version 9.1.

  1. Low-frequency vibrational spectra of crystals of tutton salts

    Science.gov (United States)

    Barashkov, M. V.; Zazhogin, A. A.; Komyak, A. I.; Shashkov, S. N.

    2000-07-01

    IR absorption spectra and polarized Raman spectra of crystals of Tutton salts K2M(SO4)26H2O and (NH4)2M(SO4)2·6H2O, where M=Co, Ni, Zn, have been obtained by experiment at 93 K and at room temperature. The frequencies and forms of normal modes of the [Zn(H2O)6]2+ octahedral complex have been calculated. The observed lines are assigned to the internal modes of the [M(H2O)6]2+ complex and external modes of the crystal lattice in accordance with the results of the calculations and factor-group analysis.

  2. The mechanical spectra of deposited materials by a composite reed vibration method

    International Nuclear Information System (INIS)

    Ying, X.N.; Zhang, L.; Yuan, Y.H.

    2010-01-01

    Recently a composite reed vibration method has been designed to measure the mechanical spectra (complex Young's modulus) of materials from liquid to solid state. The mechanical spectra of materials can be obtained from a composite system consisting of a substrate reed and of materials deposited on it. In this report, two sets of formulas to calculate the mechanical spectra of deposited materials are further analyzed. The proof is given for the previous named 'approximate formulas' (labeled as Formula II). Then the composite reed vibration method can be safely used as an extension of the mechanical spectrum method of the thin solid film. At the same time, some comments are made on previous analytical formulas (labeled as Formula I). At last, more experiments with a small amount of deposited materials are performed. It is found that smaller quantity is more favorable to achieve the intrinsic mechanical spectra of deposited materials.

  3. Electronic and vibrational circular dichroism spectra of (R)-(−)-apomorphine

    International Nuclear Information System (INIS)

    Abbate, Sergio; Longhi, Giovanna; Lebon, France; Tommasini, Matteo

    2012-01-01

    Highlights: ► ECD and VCD Spectra of (R)-(−)-apomorphine measured in various solvents. ► DFT calculations allow to study the protonation state and conformations. ► Contributions from catechol OH vibrations to the VCD spectra is studied. -- Abstract: Apomorphine is a chiral drug molecule; notwithstanding its extraordinary importance, little attention has been paid to the characterization of its chiroptical properties. Here we report on its electronic circular dichroism (ECD) spectra, recorded in methanol and water, and vibrational circular dichroism (VCD) in methanol and dimethyl sulfoxide (DMSO) solutions. Density functional theory (DFT) calculations have allowed us to interpret the spectra and to evaluate the role of possible conformations, charge-states and interactions with counter ions.

  4. Vibrational spectra of double rare earth alkaline metal metaphosphates

    International Nuclear Information System (INIS)

    Madij, V.A.; Krasilov, Yu.I.; Kizel', V.A.; Denisov, Yu.V.; Chudinova, N.N.; Vinogradova, N.V.

    1978-01-01

    Joint analysis of the Raman and infrared absorption spectra, as well as X-ray structural data for binary metaphosphates, suggest a cyclic structure of the anion in RbEu(PO 3 ) 4 and a chain structure of the anions in HEu(PO 3 ) 4 and LiEu(PO 3 ) 4 . Spectroscopic criteria are proposed for distinguishing between cyclic and chain structures in binary metaphosphates of rare earth elements and alkali metals

  5. 2D fluorescence spectra measurement of six kinds of bioagents simulants by short range Lidar

    Science.gov (United States)

    Sanpedro, Man

    2018-02-01

    Pantoea agglomerans (Pan), Staphylococcus aureus (Sta), Bacillus globigii (BG) and Escherichia coli (EH), these four kinds of bioagents simulants of were cultured and then their growth curves were measured, the generation time was 0.99h, 0.835h, 1.07h and 1.909h, respectively. A small short range fluorescence lidar working at wavelengths of 266nm and 355nm was designed and used to measure the two-dimensional fluorescence spectra of bioagents simulants in the amino acid segment and NADH segment, respectively. In a controllable fluorescence measurement chamber, the two-dimensional fluorescence spectra of vegetative liquid bacterial aerosols as well as BSA and OVA, two protein toxinic simulants were measured with a resolution of 4nm. The two-dimensional fluorescence spectral shape of Pan, Sta, EH and BG, BSA and OVA were consistent with the standard fluorescent component tryptophan in the amino acid band with FWHM of 60nm, but the central wavelength of the fluorescence spectra of these simulants blue/purple shifted obviously as affected by the external biochemical environment, concentration and ratio of different bacterial internal fluorophores, so the energy level between the excited state and the ground state of the fluorescence molecule increased. Differently, weak NADH fluorescence spectra with 100nm FWHM inside the four vegetative bacteria aerosols were detected, but Rayleigh scattering, Raman scattering contribution of water, nitrogen in the fluorescence spectra could not be effectively extracted. The second - order derivative fluorescence spectra of four simulants showed that the high - order processing and recognition of the fluorescence spectra was feasible.

  6. Vibrational spectra of N-butyryl-homoserine lactone

    DEFF Research Database (Denmark)

    Bak, J.

    A special class of organic compounds, N-acyl homoserine lactones (HSL), is synthesized in bacteria and takes part in the intercellular signaling designated quorum sensing. The outcome of the intercellular signaling is responsible for many of the interesting properties which characterize colony...... for a substantial part of morbidity and mortality in many medical specialties. Lactones are also interesting compounds from a spectroscopic point of view. The spectroscopic information about these compounds in the literature is very sparse. In this study we present the Mid-infrared spectra of homoserine lactones...

  7. Vibrational spectra of the cyanodimethylmetal complexes of magnesium, aluminium, gallium, and indium

    International Nuclear Information System (INIS)

    Mueller, J.; Schmock, F.; Klopsch, A.; Dehnicke, K.

    1975-01-01

    Tetramethylammonium cyanide reacts with an ethereal solution of dimethylmagnesium to form [NMe 4 ] 4 [Me 2 MgCN] 4 , the complex anion of which is isoelectronic with the known tetrameric dimethylaluminium cyanide [Me 2 AlCN] 4 . The vibrational spectra are reported together with those of the corresponding gallium and indium compounds. (orig.) [de

  8. Diagnosis of faults in rolling element bearings by using directional spectra of vibration signals

    International Nuclear Information System (INIS)

    Park, Jong Po; Lee, Chong Won

    1999-01-01

    Backward and forward defect frequencies of rolling element bearing are experimentally investigated utilizing the two-sided directional spectra of the complex-valued vibration signals measured from the outer ring of defective bearings. The experimental results show that the directional zoom spectrum is superior to the conventional spectrum in identification of bearing defect frequencies, in particular the inner race defect frequencies

  9. Rotation-vibrational spectra of diatomic molecules and nuclei with Davidson interactions

    CERN Document Server

    Rowe, D J

    1998-01-01

    Complete rotation-vibrational spectra and electromagnetic transition rates are obtained for Hamiltonians of diatomic molecules and nuclei with Davidson interactions. Analytical results are derived by dynamical symmetry methods for diatomic molecules and a liquid-drop model of the nucleus. Numerical solutions are obtained for a many-particle nucleus with quadrupole Davidson interactions within the framework of the microscopic symplectic model. (author)

  10. The study of crystal structures and vibrational spectra of inorganicsalts of 2,4-diaminopyrimidine

    Czech Academy of Sciences Publication Activity Database

    Matulková, I.; Mathauserová, J.; Císařová, I.; Němec, I.; Fábry, Jan

    2016-01-01

    Roč. 1103, Jan (2016), s. 82-93 ISSN 0022-2860 R&D Projects: GA ČR GA14-05506S Institutional support: RVO:68378271 Keywords : salts of 2,4-diaminopyrimidine * single crystal X-ray structural analysis * vibrational spectra Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.753, year: 2016

  11. Ab initio and DFT studies of the structure and vibrational spectra of anhydrous caffeine

    Science.gov (United States)

    Srivastava, Santosh K.; Singh, Vipin B.

    2013-11-01

    Vibrational spectra and molecular structure of anhydrous caffeine have been systematically investigated by second order Moller-Plesset (MP2) perturbation theory and density functional theory (DFT) calculations. Vibrational assignments have been made and many previous ambiguous assignments in IR and Raman spectra are amended. The calculated DFT frequencies and intensities at B3LYP/6-311++G(2d,2p) level, were found to be in better agreement with the experimental values. It was found that DFT with B3LYP functional predicts harmonic vibrational wave numbers more close to experimentally observed value when it was performed on MP2 optimized geometry rather than DFT geometry. The calculated TD-DFT vertical excitation electronic energies of the valence excited states of anhydrous caffeine are found to be in consonance to the experimental absorption peaks.

  12. Study on fluorescence spectra of thiamine, riboflavin and pyridoxine

    Science.gov (United States)

    Yang, Hui; Xiao, Xue; Zhao, Xuesong; Hu, Lan; Lv, Caofang; Yin, Zhangkun

    2016-01-01

    This paper presents the intrinsic fluorescence characteristics of vitamin B1, B2 and B6 measured with 3D fluorescence Spectrophotometer. Three strong fluorescence areas of vitamin B2 locate at λex/λem=270/525nm, 370/525nm and 450/525nm, one fluorescence areas of vitamin B1 locates at λex/λem=370/460nm, two fluorescence areas of vitamin B6 locate at λex/λem=250/370nm and 325/370nm were found. The influence of pH of solution to the fluorescence profile was also discussed. Using the PARAFAC algorithm, 10 vitamin B1, B2 and B6 mixed solutions were successfully decomposed, and the emission profiles, excitation profiles, central wavelengths and the concentration of the three components were retrieved precisely through about 5 iteration times.

  13. Analysis of molecular structure and vibrational spectra of hexadecyl (cetyl) trimethylammonium brode (CTAB)

    International Nuclear Information System (INIS)

    Goekce, H.; Bahceli, S.

    2010-01-01

    FT-IR and Raman spectra of CTAB [C 1 6H 3 3N(CH 3 ) 3 ] + Br - have been experimentally recorded in the region 550-4000 cm - 1 and 400-3100 cm - 1, respectively. The molecular geometry and vibrational frequencies of CTAB in the ground state have been calculated by using ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with the 6-31+G(d,p) basis set. The obtained optimized geometric parameters (bond lengths and bond angles) and vibrational frequencies were in very good agreement with the experimental data. The comparisons of the observed fundamental vibrational frequencies and calculated results for the fundamental vibrational frequencies of CTAB shows that the scaled B3LYP method is superior compared to the scaled HF method.

  14. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    Science.gov (United States)

    2016-06-03

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited -State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited -State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited -state

  15. [Study on the vibrational spectra and XRD characters of Huanglong jade from Longling County, Yunnan Province].

    Science.gov (United States)

    Pei, Jing-cheng; Fan, Lu-wei; Xie, Hao

    2014-12-01

    Based on the conventional test methods, the infrared absorption spectrum, Raman spectrum and X-ray diffraction (XRD) were employed to study the characters of the vibration spectrum and mineral composition of Huanglong jade. The testing results show that Huanglong jade shows typical vibrational spectrum characteristics of quartziferous jade. The main infrared absorption bands at 1162, 1076, 800, 779, 691, 530 and 466 cm(-1) were induced by the asymmetric stretching vibration, symmetrical stretching vibration and bending vibration of Si-O-Si separately. Especially the absorption band near 800 cm(-1) is split, which indicates that Huanglong jade has good crystallinity. In Raman spectrum, the main strong vibration bands at 463 and 355 cm(-1) were attributed to bending vibration of Si-O-Si. XRD test confirmed that Quartz is main mineral composition of Huanglong jade and there is a small amount of hematite in red color samples which induced the red color of Huanglong jade. This is the first report on the infrared, Raman and XRD spectra feature of Huanglong jade. It will provide a scientific basis for the identification, naming and other research for huanglong jade.

  16. Assisted Interpretation of Laser-Induced Fluorescence Spectra of Egg-Based Binding Media Using Total Emission Fluorescence Spectroscopy

    International Nuclear Information System (INIS)

    Anglos, D.; Nevin, A.

    2006-01-01

    Laser-induced fluorescence (LIF) spectroscopy can provide nondestructive, qualitative analysis of protein-based binding media found in artworks. Fluorescence emissions from proteins in egg yolk and egg white are due to auto fluorescent aromatic amino acids as well as other native and age-related fluorophores, but the potential of fluorescence spectroscopy for the differentiation between binding media is dependent on the choice of a suitable excitation wavelength and limited by problems in interpretation. However, a better understanding of emission spectra associated with LIF can be achieved following comparisons with total emission fluorescence spectra where a series of consecutive emission spectra are recorded over a specific range. Results using nanosecond UV laser sources for LIF of egg-based binding media are presented which are rationalised following comparisons with total emission spectra. Specifically, fluorescence is assigned to tryptophan and oxidation products of amino acids; in the case of egg yolk, fatty-acid polymerisation and age-related degradation products account for the formation of fluorophores.

  17. Two Dimensional Multiwavelength Fluorescence Spectra of Dipicolinic Acid and Calcium Dipicolinate

    National Research Council Canada - National Science Library

    Sarasanandarajah, Sivananthan

    2004-01-01

    .... In this paper we report in some detail on the room temperature fluorescence excitation and emission spectra of DPA and its calcium ion complex and comparison of the excitation-emission spectrum...

  18. Effect of surfactants on the fluorescence spectra of water-soluble ...

    Indian Academy of Sciences (India)

    TECS

    Effect of surfactants on the fluorescence spectra of water-soluble. MEHPPV ... polyacrylic acid (PAA) chains grafted onto their backbone were found to be water soluble, and they exhi- ..... in other words the variation of emission intensity.

  19. Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer

    Science.gov (United States)

    Tiwari, Vivek; Jonas, David M.

    2018-02-01

    Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Förster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a

  20. Vibronic-structure tracking: A shortcut for vibrationally resolved UV/Vis-spectra calculations

    Energy Technology Data Exchange (ETDEWEB)

    Barton, Dennis; König, Carolin; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany)

    2014-10-28

    The vibrational coarse structure and the band shapes of electronic absorption spectra are often dominated by just a few molecular vibrations. By contrast, the simulation of the vibronic structure even in the simplest theoretical models usually requires the calculation of the entire set of normal modes of vibration. Here, we exploit the idea of the mode-tracking protocol [M. Reiher and J. Neugebauer, J. Chem. Phys. 118, 1634 (2003)] in order to directly target and selectively calculate those normal modes which have the largest effect on the vibronic band shape for a certain electronic excitation. This is achieved by defining a criterion for the importance of a normal mode to the vibrational progressions in the absorption band within the so-called “independent mode, displaced harmonic oscillator” (IMDHO) model. We use this approach for a vibronic-structure investigation for several small test molecules as well as for a comparison of the vibronic absorption spectra of a truncated chlorophyll a model and the full chlorophyll a molecule. We show that the method allows to go beyond the often-used strategy to simulate absorption spectra based on broadened vertical excitation peaks with just a minimum of computational effort, which in case of chlorophyll a corresponds to about 10% of the cost for a full simulation within the IMDHO approach.

  1. Vibrationally resolved photoelectron spectra of lower diamondoids: A time-dependent approach

    Science.gov (United States)

    Xiong, Tao; Włodarczyk, Radosław; Gallandi, Lukas; Körzdörfer, Thomas; Saalfrank, Peter

    2018-01-01

    Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ˜0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].

  2. Measurements of the Ultraviolet Fluorescence Cross Sections and Spectra of Bacillus Anthracis Simulants

    Energy Technology Data Exchange (ETDEWEB)

    Stephens, J.R.

    1998-09-01

    Measurements of the ultraviolet autofluorescence spectra and absolute cross sections of the Bacillus anthracis (Ba) simulants Bacillus globigii (Bg), Bacillus megaterium (Bm), Bacillus subtilis (Bs), and Bacillus cereus (Bc) were measured. Fluorescence spectra and cross sections of pine pollen (Pina echinata) were measured for comparison. Both dried vegetative cells and spores separated from the sporulated vegetative material were studied. The spectra were obtained by suspending a small number (<10) of particles in air in our Single Particle Spectroscopy Apparatus (SPSA), illuminating the particles with light from a spectrally filtered arc lamp, and measuring the fluorescence spectra of the particles. The illumination was 280 nm (20 nm FWHM) and the fluorescence spectra was measured between 300 and 450 nm. The fluorescence cross section of vegetative Bg peaks at 320 nm with a maximum cross section of 5 X 10{sup -14} cm{sup 2}/sr-nm-particle while the Bg spore fluorescence peaks at 310 nm with peak fluorescence of 8 X 10{sup -15} cm{sup 2}/sr-nm-particle. Pine pollen particles showed a higher fluorescence peaking at 355 nm with a cross section of 1.7 X 10{sup -13} cm{sup 2}/sr-nm-particle. Integrated cross sections ranged from 3.0 X 10{sup -13} for the Bg spores through 2.25 X 10{sup -12} (cm{sup 2}/sr-particle) for the vegetative cells.

  3. 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.

  4. Attempt to separate the fluorescence spectra of adrenaline and noradrenaline using chemometrics

    DEFF Research Database (Denmark)

    Nikolajsen, Rikke P; Hansen, Åse Marie; Bro, R

    2000-01-01

    An investigation was conducted on whether the fluorescence spectra of the very similar catecholamines adrenaline and noradrenaline could be separated using chemometric methods. The fluorescence landscapes (several excitation and emission spectra were measured) of two data sets with respectively 16...... regression (Unfold-PLSR) on the larger data set and parallel factor analysis (PARAFAC) of the six samples of the smaller set showed that there was no difference between the fluorescence landscapes of adrenaline and noradrenaline. It can be concluded that chemometric separation of adrenaline and noradrenaline...

  5. Quantitative Interpretation of Polarization SFG Vibrational Spectra of Air/Methanol Interface

    Science.gov (United States)

    Wu, Hui; Zhang, Wen-kai; Gan, Wei; Cui, Zhi-feng; Wang, Hong-fei

    2006-06-01

    Even though in IR and Raman spectra of liquid methanol there is always an apparent feature for the asymmetric stretching mode of the CH3 group around 2970 cm-1, this feature has not been observed in the Sum Frequency Generation Vibrational Spectroscopy (SFG-VS) in any polarizations from the air/methanol interface. Here we present a treatment based on a corrected bond additivity model to quantitatively interpret the SFG-VS of the air/methanol interface from the IR and Raman spectra of liquid methanol.

  6. Melanin fluorescence spectra by step-wise three photon excitation

    Science.gov (United States)

    Lai, Zhenhua; Kerimo, Josef; DiMarzio, Charles A.

    2012-03-01

    Melanin is the characteristic chromophore of human skin with various potential biological functions. Kerimo discovered enhanced melanin fluorescence by stepwise three-photon excitation in 2011. In this article, step-wise three-photon excited fluorescence (STPEF) spectrum between 450 nm -700 nm of melanin is reported. The melanin STPEF spectrum exhibited an exponential increase with wavelength. However, there was a probability of about 33% that another kind of step-wise multi-photon excited fluorescence (SMPEF) that peaks at 525 nm, shown by previous research, could also be generated using the same process. Using an excitation source at 920 nm as opposed to 830 nm increased the potential for generating SMPEF peaks at 525 nm. The SMPEF spectrum peaks at 525 nm photo-bleached faster than STPEF spectrum.

  7. Vibrational spectra of four-coordinated random networks with periodic boundary conditions

    International Nuclear Information System (INIS)

    Guttman, L.

    1976-01-01

    Examples of perfectly four-coordinated networks satisfying periodic boundary conditions are constructed by a pseudo-random process, starting from a crystalline region. The unphysical features (high density, large deviations from the tetrahedral bond-angle) are removed by systematic modification of the bonding scheme. The vibrational spectra are calculated, using a valence-force potential, and the neutron scattering is computed by a phonon-expansion approximation

  8. Study on serum fluorescence spectra based on wavelet transform

    African Journals Online (AJOL)

    STORAGESEVER

    2010-02-08

    Feb 8, 2010 ... Blood plays an important role in clinical diagnosis and treatment and as such, the analysis of blood spectrum will be of very important practical significance. Serum fluorescence emission intensity is closely related with the excitation wavelength; when the excitation wavelength is 230 nm, the blood.

  9. Study on serum fluorescence spectra based on wavelet transform ...

    African Journals Online (AJOL)

    Blood plays an important role in clinical diagnosis and treatment and as such, the analysis of blood spectrum will be of very important practical significance. Serum fluorescence emission intensity is closely related with the excitation wavelength; when the excitation wavelength is 230 nm, the blood lipid concentration and ...

  10. Different level of fluorescence in Raman spectra of montmorillonites

    Czech Academy of Sciences Publication Activity Database

    Ritz, M.; Vaculíková, Lenka; Kupková, J.; Plevová, Eva; Bartoňová, L.

    2016-01-01

    Roč. 84, May 2016 (2016), s. 7-15 ISSN 0924-2031 R&D Projects: GA MŠk(CZ) LO1406; GA MŠk ED2.1.00/03.0082 Institutional support: RVO:68145535 Keywords : Raman spectroscopy * fluorescence * montmorillonite Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.740, year: 2016

  11. Fluorescence spectra of bithiophene and terthiophene single crystals and of their isolated molecules in cyclodextrin

    International Nuclear Information System (INIS)

    Gombojav, Bold; Namsrai, Nasanbat; Yoshinari, Takehisa; Nagasaka, Shin-ichiro; Itoh, Hiroki; Koyama, Kiyohito

    2004-01-01

    In order to examine the effect of subsumption space of β- and γ-cyclodextrin (CyD) on the photophysics of oligothiophenes, 2, 2'-bithiophene (BT) and 2, 2': 5', 2''-terthiophene (TT), the fluorescence spectra were compared with those of the single crystals (SC) at 15, 77 K and room temperature (RT). Both the numbers of BT included in β- and γ-CyD are twin (BT 2 ). The numbers of TT included in β- and γ-CyD are unit (TT 1 ) and twin (TT 2 ), respectively. Electronic excitation of BT encapsulated in β- and γ-CyD gives similar fluorescence spectra, showing bathochromic shift compared with that of BT single crystal, (BT) SC . The observation that the fluorescence spectra of encapsulated BT 2 are similar to the spectra of its THF solution suggests the configuration of BT 2 in β- and γ-CyD should be face-to-face configuration (BT 2 ) parrallel . On the contrary, TT in β- and in γ-CyD afford quite different fluorescence spectra. Encapsulated TT in β-CyD exhibits the hypsochromic shift of fluorescence maxima compared to that of TT single crystal, (TT) SC . While the bathochromically shifted fluorescence spectra of TT 2 in γ-CyD is also ascribed to the face-to-face configuration (TT 2 ) parallel as in the case of BT 2 in γ-CyD. Fluorescence spectra show the excited ground state complex of BT 2 and TT 2 in γ-CyD

  12. Vibrational spectra, powder X-ray diffractions and physical properties of cyanide complexes with 1-ethylimidazole

    Science.gov (United States)

    Kürkçüoğlu, Güneş Süheyla; Kiraz, Fulya Çetinkaya; Sayın, Elvan

    2015-10-01

    The heteronuclear tetracyanonickelate(II) complexes of the type [M(etim)Ni(CN)4]n (hereafter, abbreviated as M-Ni-etim, M = Mn(II), Fe(II) or Co(II); etim = 1-ethylimidazole, C5H8N2) were prepared in powder form and characterized by FT-IR and Raman spectroscopy, powder X-ray diffraction (PXRD), thermal (TG; DTG and DTA), and elemental analysis techniques. The structures of these complexes were elucidated using vibrational spectra and powder X-ray diffraction patterns with the peak assignment to provide a better understanding of the structures. It is shown that the spectra are consistent with a proposed crystal structure for these compounds derived from powder X-ray diffraction measurements. Vibrational spectra of the complexes were presented and discussed with respect to the internal modes of both the etim and the cyanide ligands. The C, H and N analyses were carried out for all the complexes. Thermal behaviors of these complexes were followed using TG, DTG and DTA curves in the temperature range 30-700 °C in the static air atmosphere. The FT-IR, Raman spectra, thermal and powder X-ray analyses revealed no significant differences between the single crystal and powder forms. Additionally, electrical and magnetic properties of the complexes were investigated. The FT-IR and Raman spectroscopy, PXRD, thermal and elemental analyses results propose that these complexes are similar in structure to the Hofmann-type complexes.

  13. Temperature dependent analysis of three classes of fluorescence spectra from p-6P nanofiber films

    DEFF Research Database (Denmark)

    Balzer, F.; Pogantsch, Alexander; Rubahn, Horst-Günter

    2009-01-01

    devices, given that the spectra are reproducible for varying surface temperatures. A detailed investigation as a function of surface temperature variation from 300 to 30 K reveals three classes of spectra: (a) spectra with well resolved excitonic peaks, which shift 35meV to the blue with decreasing...... temperature, (b) similar spectra with an additional intermediate broadening around 150 K, and (c) excitonic spectra similar to (b), but with a green defect emission band. Quantitative fitting of type (a) spectra results in an  exciton–phonon coupling factor of 80 ± 10meV and an average phonon temperature of Θ...... = 670 ± 70 K. The Huang–Rhys factor decreases linearly from 1.2 at 300 K to 1.0 at 30 K. Fitting of type (b) spectra reveals that the apparent intermediate temperature broadening is due to additional fluorescence peaks, the relative importance of which increasing with decreasing temperature....

  14. Fluorescence spectra of blood plasma treated with ultraviolet irradiation in vivo

    Science.gov (United States)

    Zalesskaya, G. A.; Maslova, T. O.

    2010-09-01

    We have studied the fluorescence spectra of blood plasma from patients with acute coronary syndrome, and also the effect of therapeutic doses of in vivo ultraviolet blood irradiation (UBI) on the spectra. We have established that the maxima in the fluorescence spectra of the original plasma samples, obtained from unirradiated blood, are located in the wavelength interval 330-340 nm, characteristic for the fluorescence of tryptophan residues. In extracorporeal UBI ( λ = 254 nm), we observed changes in the shape and also both a blue and a red shift in the maxima of the fluorescence spectra, differing in magnitude for blood plasma samples from different patients in the test group. We show that UBI-initiated changes in the fluorescence spectra of the plasma depend on the original pathological disturbances of metabolite levels, and also on the change in the oxygen-transport function of the blood and the acid-base balance, affecting the oxidative stability of the plasma. We have concluded that UV irradiation, activating buffer systems in the blood, has an effect on the universal and specific interactions of the tryptophan residue with the amino acid residues and water surrounding it.

  15. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2013-05-10

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  16. Thermo-dynamical contours of electronic-vibrational spectra simulated using the statistical quantum-mechanical methods

    DEFF Research Database (Denmark)

    Pomogaev, Vladimir; Pomogaeva, Anna; Avramov, Pavel

    2011-01-01

    Three polycyclic organic molecules in various solvents focused on thermo-dynamical aspects were theoretically investigated using the recently developed statistical quantum mechanical/classical molecular dynamics method for simulating electronic-vibrational spectra. The absorption bands of estradiol...

  17. Experimental Studies of Laser-Induced Fluorescence Spectra of Plants Immunity to the Kind of Ground

    Directory of Open Access Journals (Sweden)

    Yu. V. Fedotov

    2015-01-01

    Full Text Available Various external factors (pollutants available in the soil, a lack or insufficient amount of water and nutrients, etc. lead to stressful conditions of plants and impossibility of their normal development. At the early stages it is difficult to identify visually the stressful situations of plants. Therefore development of methods and devices to detect stressful states is important.A method of the laser-induced fluorescence is one of perspective methods for detection of stressful conditions of plants.In spite of quite a great number of work presenting results of the pilot studies of fluorescence spectra of vegetation, there are some important issues, which are unclear.The paper gives results of pilot studies of stability of a spectrum form of the laser-induced fluorescence of plants for different types of soil at the wavelength of excitation fluorescence of 532 nm.Results of processing fluorescence spectra of plants show:- fluorescence spectra of plants grown up under similar conditions have good repeatability of a spectra form for different samples of plants and different measurement time for each type of studied soil. The ratio value R of the fluorescence intensity at the wavelength of 685 nm to the fluorescence intensity at the wavelength of 740 nm has high stability. The standard deviation in sampling of the ratio R of different samples of a plant for one type of soil (for width of spectral ranges of recording fluorescent radiation of 10 nm lies in the range ~ 0.055 - ~ 0.12;- a difference in plant fluorescence spectra between themselves for different types of soil has the same order as a difference in fluorescence spectra of different samples of a plant for one type of soil. Difference in average value of the ratio R for different types of soil lies in the range ~ 0.01 - ~ 0.15.Thus, the value of the ratio R is steady against a type of soil and can be used to control a condition of plants.

  18. Comparative studies on molecular structure, vibrational spectra and hyperpolarizabilies of NLO chromophore Ethyl 4-Dimethylaminobenzoate

    Science.gov (United States)

    Amalanathan, M.; Jasmine, G. Femina; Roy, S. Dawn Dharma

    2017-08-01

    The molecular structure, vibrational spectra and polarizabilities of Ethyl 4-Dimethylaminobenzoate (EDAB) was investigated by density functional theory employing Becke's three parameter hybrid exchange functional with Lee-Yang-Parr (B3LYP) co-relational functional involving 6-311++G(d,p) basis set and compared with some other levels. A detailed interpretation of the IR and Raman spectra of EDBA have been reported and analyzed. Complete vibrational assignments of the vibrational modes have been done on the basis of the potential energy distribution (TED) using VEDA software. The molecular electrostatic potential mapped onto total density surface has been obtained. A study on the electronic properties, such as absorption wavelength, and frontier molecular orbitals energy, was performed using DFT approach. The stability of the molecule arising from hyper conjugative interactions and accompanying charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The natural and Mulliken charge also calculated and compared with different level of calculation. The dipole moment, polarizability and first, second order hyperpolarizabilities of the title molecule were calculated and compared with the experimental values. The energy gap between frontier orbitals has been used along with electric moments and first order hyperpolarizability, to understand the non linear optical (NLO) activity of the molecule. The NLO activity of molecule was confirmed by SHG analysis.

  19. Experimental and theoretical study on the structure and vibrational spectra of β-2-aminopyridinium dihydrogenphosphate

    Science.gov (United States)

    Çırak, Çağrı; Demir, Selçuk; Ucun, Fatih; Çubuk, Osman

    2011-08-01

    Experimental and theoretical vibrational spectra of β-2-aminopyridinium dihydrogenphosphate (β-2APDP) have been investigated. The FT-IR spectrum of β-2APDP was recorded in the region 4000-400 cm -1. The optimized molecular structure and theoretical vibrational frequencies of β-2APDP have been investigated using ab initio Hartree-Fock (HF) and density functional B3LYP method with 6-311++G(d,p) basis set. The optimized geometric parameters (bond lengths and bond angles) and theoretical frequencies have been compared with the corresponding experimental data and it is found that they agree well with each other. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Furthermore, the used scale factors were obtained from the ratio of the frequency values of the strongest peaks in the experimental and theoretical IR spectra. From the results it was concluded that the B3LYP method is superior to the HF method for the vibrational frequencies.

  20. CN molecule vibrational spectra excitation in several LTE plasma sources conditions

    International Nuclear Information System (INIS)

    Iova, I.; Iova, Floriana; Ionita, I.; Bazavan, M.; Ilie, Gh.; Stanescu, G.

    2001-01-01

    Our interest in CN plasma study steams of the facilities to obtain the CN radicals in a free atmosphere electric discharge where the C of the coal electrodes can to combine in the enough high temperature plasma with the atmospheric nitrogen. Also of much interest is the very important phenomena in which the CN vibrational spectra can be implied and used as a diagnostic tool (plasma chemistry, astrophysics and so on). A peculiar importance presents the CN vibrational spectra in the transient plasmas. It is the reason why we have investigated here some internal processes of a continued and interrupted arc of various pulse lengths. To these purposes we present with enough accuracy the behaviour of the relative band head intensities of the sequences Δ v = +1 and Δ v = 0 belonging to the CN electronic transition (B 2 Σ - X 2 Σ), as a function of the pulse length (50 - 200 ms) as well as a function of the cathode to anode separation. These behaviours give us indications on the vibrational levels of the electronic state populations in several regions of the arc plasma as well on the efficiency of these levels excitation for several plasma pulse lengths. (authors)

  1. Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

    Science.gov (United States)

    Alver, Özgur; Kaya, Mehmet Fatih

    2014-11-01

    Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.

  2. Vibrational spectra and natural bond orbital analysis of organic crystal L-prolinium picrate

    Science.gov (United States)

    Edwin, Bismi; Amalanathan, M.; Hubert Joe, I.

    2012-10-01

    Vibrational spectral analysis and quantum chemical computations based on density functional theory (DFT) have been performed on the organic crystal L-prolinium picrate (LPP). The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers of LPP have been investigated using B3LYP method. The calculated molecular geometry has been compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA 4 program. The various intramolecular interactions confirming the biological activity of the compound have been exposed by natural bond orbital analysis. The distribution of Mulliken atomic charges and bending of natural hybrid orbitals associated with hydrogen bonding also reflects the presence of intramolecular hydrogen bonding thereby enhancing bioactivity. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and low value of energy gap indicates electron transport in the molecule and thereby bioactivity. Vibrational analysis reveals the presence of strong O-H⋯O and N-H⋯O interaction between L-prolinium and picrate ions providing evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity.

  3. DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol

    Science.gov (United States)

    Renuga Devi, T. S.; Sharmi kumar, J.; Ramkumaar, G. R.

    2014-12-01

    The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400 cm-1 and 4000-50 cm-1 respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results.

  4. Envelope method for background elimination from X-ray fluorescence spectra

    International Nuclear Information System (INIS)

    Monakhov, V.V.; Naumenko, P.A.; Chashinskaya, O.A.

    2006-01-01

    The influence of the background noise caused by Bremsstrahlung on the accuracy of the envelope method at x-ray fluorescence spectra processing is studied. This is carried out by the example of model spectra at different forms of Bremsstrahlung noise as well as at the presence of background noise in spectra. The interpolation by parabolic splines is used for the estimation of the error of the envelope method for the elimination of continuos background noise. It is found out that the error of the proposed method constitutes decimal parts of percent. It is shown that the envelope method is the effective technique for the elimination of the continuous Bremsstrahlung from x-ray fluorescence spectra of the first order [ru

  5. Nightmare from which you will never awake: Electronic to vibrational spectra!

    Energy Technology Data Exchange (ETDEWEB)

    De Silva, Nuwon [Iowa State Univ., Ames, IA (United States)

    2013-01-01

    The theoretical background of ab initio methods and density functional theory is provided. The anharmonicity associated with weakly bound metal cation dihydrogen complexes is examined using the vibrational self-consistent field (VSCF) method and the interaction between a hydrogen molecule and a metal cation is characterized. A study of molecular hydrogen clustering around the lithium cation and their accompanied vibrational anharmonicity employing VSCF is illustrated. A qualitative interpretation is provided of solvent-induced shifts of amides and simulated electronic absorption spectra using the combined time-dependent density functional theory/effective fragment potential method (TDDFT/EFP). An excited-state solvent assisted quadruple hydrogen atom transfer reaction of a coumarin derivative is elucidated using micro solvated quantum mechanical (QM) water and macro solvated EFP water. A dispersion correction to the QM-EFP1 interaction energy is presented.

  6. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X 1Ag ↔ A1B1u absorption and fluorescence spectra of perylene

    International Nuclear Information System (INIS)

    Wang, Chen-Wen; Zhu, Chaoyuan; Lin, Sheng-Hsien; Yang, Ling; Yu, Jian-Guo

    2014-01-01

    Damped harmonic oscillators are utilized to calculate Franck-Condon factors within displaced harmonic oscillator approximation. This is practically done by scaling unperturbed Hessian matrix that represents local modes of force constants for molecule in gaseous phase, and then by diagonalizing perturbed Hessian matrix it results in direct modification of Huang–Rhys factors which represent normal modes of solute molecule perturbed by solvent environment. Scaling parameters are empirically introduced for simulating absorption and fluorescence spectra of an isolated solute molecule in solution. The present method is especially useful for simulating vibronic spectra of polycyclic aromatic hydrocarbon molecules in which hydrogen atom vibrations in solution can be scaled equally, namely the same scaling factor being applied to all hydrogen atoms in polycyclic aromatic hydrocarbons. The present method is demonstrated in simulating solvent enhanced X 1 A g ↔ A 1 B 1u absorption and fluorescence spectra of perylene (medium-sized polycyclic aromatic hydrocarbon) in benzene solution. It is found that one of six active normal modes v 10 is actually responsible to the solvent enhancement of spectra observed in experiment. Simulations from all functionals (TD) B3LYP, (TD) B3LYP35, (TD) B3LYP50, and (TD) B3LYP100 draw the same conclusion. Hence, the present method is able to adequately reproduce experimental absorption and fluorescence spectra in both gas and solution phases

  7. COLORED DISSOLVED ORGANIC MATTER (CDOM) CHARACTERIZATION BY ABSORPTION AND FLUORESCENCE SPECTRA

    OpenAIRE

    Goncalves Araujo, Rafael; Ramirez-Perez, Marta; Kraberg, Alexandra; Piera, Jaume; Bracher, Astrid

    2014-01-01

    Colored dissolved organic matter (CDOM) absorption and fluorescence spectra were analyzed from samples collected in the Lena River Delta region (Siberia, Russia; summer-2013) and in the Alfacs Bay (Ebro River Delta, Spain; summer-2013/winter-2014) in order to use optical measurements to infer loading and origin of CDOM. Absorbance spectra and Excitation-Emission matrices (EEMs) were obtained with a HORIBA Aqualog® spectrofluorometer. CDOM absorption at 443nm (a443) and terrestrial absorption ...

  8. Fluorescence spectra of Rhodamine 6G for high fluence excitation laser radiation

    CERN Document Server

    Hung, J; Olaizola, A M

    2003-01-01

    Fluorescence spectral changes of Rhodamine 6G in ethanol and glycerol solutions and deposited as a film on a silica surface have been studied using a wide range of pumping field fluence at 532 nm at room temperature. Blue shift of the fluorescence spectra and fluorescence quenching of the dye molecule in solution are observed at high excitation fluence values. Such effects are not reported for the film sample. The effects are interpreted as the result of population redistribution in the solute-solvent molecular system induced by the high fluence field and the fluence dependence of the radiationless decay mechanism.

  9. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    Science.gov (United States)

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

  10. Two-phonon absorption spectra and lattice vibration anisotropy in HfS2

    International Nuclear Information System (INIS)

    Riede, V.; Neumann, H.; Sobotta, H.

    1983-01-01

    The infrared absorption spectra for E-vector perpendicular to c-vector in the two-phonon combination mode range is measured and analysed in order to get additional information about the A/sub 2u/ mode frequencies in HfS 2 . The lattice vibrational properties have been analysed in terms of the polarizable ion model. This model accounts for the long-range Coulomb terms of the charge and the static dipole induced by the structural anisotropy at each anion site

  11. Vibrational spectra of cholorophylls a and b labeled with 26Mg and 15N

    International Nuclear Information System (INIS)

    Lutz, M.; Kleo, J.; Gilet, R.; Henry, M.; Plus, R.; Leicknam, J.P.

    1975-01-01

    Chlorophyll molecules having their central natural magnesium replaced by 26 Mg and their natural nitrogens by 15 N were obtained by biosynthesis and examined by infrared and resonance Raman spectrometry. These observations provide unequivocal assignments of the molecular vibrational frequencies which involve the magnesium and nitrogen atoms. In particular, in both infrared and resonance Raman spectra, the absence of displacements in bands of frequency higher than 1550 cm -1 indicated the insignificant contributions of C=N stretching modes, which have maximum activity in the 1050 to 1180 cm -1 region. These results also indicate a configuration of chlorophyll in which the magnesium atom is not at a center of symmetry

  12. Fluorescent vibration-rotation excitation of cometary C2

    NARCIS (Netherlands)

    Gredel, R.; Dishoeck, van E.F.; Black, J.H.

    1989-01-01

    The statistical equilibrium equations that determine the population densities of the energy levels in cometary C2 molecules due to fluorescent excitation are examined in detail. The adopted model and molecular parameters are discussed, and a theoretical estimate is made of the two intercombination

  13. Medium-range structural properties of vitreous germania obtained through first-principles analysis of vibrational spectra.

    Science.gov (United States)

    Giacomazzi, Luigi; Umari, P; Pasquarello, Alfredo

    2005-08-12

    We analyze the principal vibrational spectra of vitreous GeO(2) and derive therefrom structural properties referring to length scales beyond the basic tetrahedral unit. We generate a model structure that yields a neutron structure factor in accord with experiment. The inelastic-neutron, the infrared, and the Raman spectra, calculated within a density-functional approach, also agree with respective experimental spectra. The accord for the Raman spectrum supports a Ge-O-Ge angle distribution centered at 135 degrees. The Raman feature X(2) is found to result from vibrations in three-membered rings, and therefore constitutes a distinctive characteristic of the medium-range structure.

  14. Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

    Science.gov (United States)

    Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

    2004-01-01

    A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

  15. Molecular structure and vibrational spectra of Bis(melaminium) terephthalate dihydrate: A DFT computational study

    Science.gov (United States)

    Tanak, Hasan; Marchewka, Mariusz K.; Drozd, Marek

    2013-03-01

    The experimental and theoretical vibrational spectra of Bis(melaminium) terephthalate dihydrate were studied. The Fourier transform infrared (FT-IR) spectra of the Bis(melaminium) terephthalate dihydrate and its deuterated analogue were recorded in the solid phase. The molecular geometry and vibrational frequencies of Bis(melaminium) terephthalate dihydrate in the ground state have been calculated by using the density functional method (B3LYP) with 6-31++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The molecule contains the weak hydrogen bonds of Nsbnd H⋯O, Nsbnd H⋯N and Osbnd H⋯O types, and those bonds are calculated with DFT method. In addition, molecular electrostatic potential, frontier molecular orbitals and natural bond orbital analysis of the title compound were investigated by theoretical calculations. The lack of the second harmonic generation (SHG) confirms the presence of macroscopic center of inversion.

  16. Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF.

    Science.gov (United States)

    Olejniczak, Iwona; Lapiński, Andrzej; Swietlik, Roman; Olivier, Jean; Golhen, Stéphane; Ouahab, Lahcène

    2011-08-01

    The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Simultaneous acquisition of pure rotational and vibrational nitrogen spectra using three-laser CARS

    International Nuclear Information System (INIS)

    Lucht, R.P.; Maris, M.A.

    1987-01-01

    The author used three-laser coherent anti-Stokes Raman scattering to acquire simultaneously the pure rotational and vibrational spectra from the nitrogen molecule. The energy level schematic for the three-laser CARS process is shown in this paper. Frequency-doubled Nd:YAG laser radiation at frequency ω/sub 1/ is used to pump a broadband dye laser which lasers at a range of frequencies ω/sub s/ and a narrowband dye laser with frequency ω/sub 2/. The three-beams are focused to a common CARS probe volume using a three-dimensional phase-matching geometry. A CARS polarization is established when the frequency difference ω/sub 1/ - ω/sub s/ corresponds to a vibrational Raman resonance. The vibrational polarization scatters the incident ω/sub 2/ beam to produce anti-Stokes radiation at frequency ω/sub 1/ - ω/sub s/ + ω/sub 2/. In a similar fashion, a CARS polarization is also established when the frequency difference ω/sub 2/ - ω/sub s/ is equal to a pure rotational Raman resonance. The pure rotational polarization scatters the Nd:YAG laser radiation at ω/sub 1/ to produce anti-Stokes radiation at ω/sub 2/ - ω/sub s/ + ω/sub 1/

  18. The temporal evolution process from fluorescence bleaching to clean Raman spectra of single solid particles optically trapped in air

    Science.gov (United States)

    Gong, Zhiyong; Pan, Yong-Le; Videen, Gorden; Wang, Chuji

    2017-12-01

    We observe the entire temporal evolution process of fluorescence and Raman spectra of single solid particles optically trapped in air. The spectra initially contain strong fluorescence with weak Raman peaks, then the fluorescence was bleached within seconds, and finally only the clean Raman peaks remain. We construct an optical trap using two counter-propagating hollow beams, which is able to stably trap both absorbing and non-absorbing particles in air, for observing such temporal processes. This technique offers a new method to study dynamic changes in the fluorescence and Raman spectra from a single optically trapped particle in air.

  19. Vibrational infrared and Raman spectra of polypeptides: Fragments-in-fragments within molecular tailoring approach

    Energy Technology Data Exchange (ETDEWEB)

    Sahu, Nityananda; Gadre, Shridhar R., E-mail: gadre@iitk.ac.in [Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016 (India)

    2016-03-21

    The present work reports the calculation of vibrational infrared (IR) and Raman spectra of large molecular systems employing molecular tailoring approach (MTA). Further, it extends the grafting procedure for the accurate evaluation of IR and Raman spectra of large molecular systems, employing a new methodology termed as Fragments-in-Fragments (FIF), within MTA. Unlike the previous MTA-based studies, the accurate estimation of the requisite molecular properties is achieved without performing any full calculations (FC). The basic idea of the grafting procedure is implemented by invoking the nearly basis-set-independent nature of the MTA-based error vis-à-vis the respective FCs. FIF has been tested out for the estimation of the above molecular properties for three isomers, viz., β-strand, 3{sub 10}- and α-helix of acetyl(alanine){sub n}NH{sub 2} (n = 10, 15) polypeptides, three conformers of doubly protonated gramicidin S decapeptide and trpzip2 protein (PDB id: 1LE1), respectively, employing BP86/TZVP, M06/6-311G**, and M05-2X/6-31G** levels of theory. For most of the cases, a maximum difference of 3 cm{sup −1} is achieved between the grafted-MTA frequencies and the corresponding FC values. Further, a comparison of the BP86/TZVP level IR and Raman spectra of α-helical (alanine){sub 20} and its N-deuterated derivative shows an excellent agreement with the existing experimental spectra. In view of the requirement of only MTA-based calculations and the ability of FIF to work at any level of theory, the current methodology provides a cost-effective solution for obtaining accurate spectra of large molecular systems.

  20. Characterization of ESIPT reactions with instant spectra of fluorescence and complexation processes

    International Nuclear Information System (INIS)

    Tomin, Vladimir I.; Ushakou, Dzmitryi V.

    2016-01-01

    Proton transfer processes and especially excited-state intramolecular proton transfer (ESIPT) are of interest not only in physical studies but in a wide range of biological and chemical researches, since they play an important role in different fundamental reactions. Moreover, occurrence of ESIPT very often causes two-bands emission spectra corresponding to the normal and photoproduct (tautomer) forms of molecular structure. It allows carrying out unique measurement of microcharacteristics in chemical and biological researches by using substances with ESIPT as molecular probes, because its dual emission is very sensitive to parameters of microenvironment. Dual fluorescence signal is very convenient for two wavelength ratiometric measurements as they are more sensitive to variations of sample characteristics. Recently new approach for revealing type of excited state reaction which is based on analysis of dynamic changes of relative intensities in instant spectra of fluorescence ESIPT solutes was suggested and tested for neat solutions. Now we generalize this method on solutions in which ESIPT solute may participate also in creating fluorescent complexes. We demonstrate that relative intensities of instant spectra of fluorescence registered with high time resolution allow to get valuable information referring to type of excited state reaction in which dye may undergo complexation reactions with ions in solvent. In addition we show how it is possible in such case to determine characteristics of complexation as, for example, stability constant and efficiency of complexation.

  1. On the purported "backbone fluorescence" in protein three-dimensional fluorescence spectra

    DEFF Research Database (Denmark)

    Bortolotti, Annalisa; Wong, Yin How; Korsholm, Stine S.

    2016-01-01

    In this study, several proteins (albumin, lysozyme, insulin) and model compounds (Trp, Tyr, homopolypeptides) were used to demonstrate the origin of the fluorescence observed upon their excitation at 220-230 nm. In the last 10 years we have observed a worrying increase in the number of articles...... as any traditional protein emission spectrum. The many papers in reputable journals erroneously reporting this peak assignment, contradicting 5 decades of prior knowledge, have led to the creation of a new dogma, where many authors and reviewers now take the purported backbone fluorescence...... as an established fact. We hope the current paper helps counter this new situation and leads to a reassessment of those papers that make this erroneous claim....

  2. Investigation of relations between skin cancer lesions' images and their fluorescent spectra

    Science.gov (United States)

    Pavlova, P.; Borisova, E.; Avramov, L.; Petkova, El.; Troyanova, P.

    2010-03-01

    This investigation is based on images obtained from healthy tissue and skin cancer lesions and their fluorescent spectra of cutaneous lesions derived after optical stimulation. Our analyses show that the lesions’ spectra of are different of those, obtained from normal tissue and the differences depend on the type of cancer. We use a comparison between these “healthy” and “unhealthy” spectra to define forms of variations and corresponding diseases. However, the value of the emitted light varies not only between the patients, but also depending on the position of the tested area inside of one lesion. These variations could be result from two reasons: different degree of damaging and different thickness of the suspicious lesion area. Regarded to the visible image of the lesion, it could be connected with the chroma of colour of the tested area and the lesion homogeneity that corresponds to particular disease. For our investigation, images and spectra of three non-melanoma cutanous malignant tumors are investigated, namely—basal cell carcinoma, squamous cell carcinoma, and keratoacanthoma. The images were processed obtaining the chroma by elimination of the background—healthy tissue, and applying it as a basic signal for transformation from RGB to Lab colorimetric model. The chroma of the areas of emission is compared with the relative value of fluorescence spectra. Specific spectral features are used to develop hybrid diagnostic algorithm (including image and spectral features) for differentiation of these three kinds of malignant cutaneous pathologies.

  3. A multi-dimensional Smolyak collocation method in curvilinear coordinates for computing vibrational spectra

    International Nuclear Information System (INIS)

    Avila, Gustavo; Carrington, Tucker

    2015-01-01

    In this paper, we improve the collocation method for computing vibrational spectra that was presented in Avila and Carrington, Jr. [J. Chem. Phys. 139, 134114 (2013)]. Using an iterative eigensolver, energy levels and wavefunctions are determined from values of the potential on a Smolyak grid. The kinetic energy matrix-vector product is evaluated by transforming a vector labelled with (nondirect product) grid indices to a vector labelled by (nondirect product) basis indices. Both the transformation and application of the kinetic energy operator (KEO) scale favorably. Collocation facilitates dealing with complicated KEOs because it obviates the need to calculate integrals of coordinate dependent coefficients of differential operators. The ideas are tested by computing energy levels of HONO using a KEO in bond coordinates

  4. Vibrational spectra of methyllithium and its aggregates: a new interpretation from ab initio anharmonic calculations

    International Nuclear Information System (INIS)

    Gohaud, Neil; Begue, Didier; Pouchan, Claude

    2005-01-01

    The complete quartic force field of methyllithium (CH 3 Li) is computed at the B3LYP/cc-pVTZ level of theory. The vibrational energy levels calculated from a perturbational and a variational procedure are in agreement with the observed spectra except for the C-Li stretching and the symmetric methyl deformation modes for which a disagreement with the experimental assignment given by Andrews is apparent. This discrepancy between experiment and theory is so large that questions are raised either about a correct characterization of, or correct calculations for the monomeric species CH 3 Li. Our theoretical study of methyllithium aggregates (CH 3 Li) n , with n = 2, 3, 4 and 6, gives a new interpretation of the experimental data

  5. Crystal structure and vibrational spectra of piperazinium bis(4-hydroxybenzenesulphonate) molecular-ionic crystal

    Science.gov (United States)

    Marchewka, M. K.; Pietraszko, A.

    2008-02-01

    The piperazinium bis(4-hydroxybenzenesulphonate) crystallizes from water solution at room temperature in P2 1/ c space group of monoclinic system. The crystals are built up of doubly protonated piperazinium cations and ionized 4-hydroxybenzenesulphonate anions that interact through weak hydrogen bonds of O-H⋯O and N-H⋯O type. Mutual orientation of anions is determined by non-conventional hydrogen bonds of C-H⋯π type. Room temperature powder FT IR and FT Raman measurements were carried out. The vibrational spectra are in full agreement with the structure obtained from X-ray crystallography. The big single crystals of the title salt can be grown.

  6. XRD, vibrational spectra and quantum chemical studies of an anticancer drug: 6-Mercaptopurine.

    Science.gov (United States)

    Kumar, S Suresh; Athimoolam, S; Sridhar, B

    2015-07-05

    The single crystal of the hydrated anticancer drug, 6-Mercaptopurine (6-MP), has been grown by slow evaporation technique under room temperature. The structure was determined by single crystal X-ray diffraction. The vibrational spectral analysis was carried out using Laser Raman and FT-IR spectroscopy in the range of 3300-100 and 4000-400 cm(-1). The single crystal X-ray studies shows that the crystal packing is dominated by N-H⋯O and O-H⋯N classical hydrogen bonds leading to a hydrogen bonded ensemble. This classical hydrogen bonds were further connected through O-H⋯S hydrogen bond to form two primary ring R4(4)(16) and R4(4)(12) motifs. These two primary ring motifs are interlinked with each other to build a ladder like structure. These ladders are connected through N-H⋯N hydrogen bond along c-axis of the unit cell through chain C(5) motifs. Further, the strength of the hydrogen bonds is studied through vibrational spectral measurements. The shifting of bands due to the intermolecular interactions was also analyzed in the solid crystalline state. Geometrical optimizations of the drug molecule were done by Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The natural bond orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical hardness, electro-negativity and chemical potential of the molecule are carried out by HOMO-LUMO plot. In which, the frontier orbitals has lower band gap value indicating the possible pharmaceutical activity of the molecule. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Automated pre-processing and multivariate vibrational spectra analysis software for rapid results in clinical settings

    Science.gov (United States)

    Bhattacharjee, T.; Kumar, P.; Fillipe, L.

    2018-02-01

    Vibrational spectroscopy, especially FTIR and Raman, has shown enormous potential in disease diagnosis, especially in cancers. Their potential for detecting varied pathological conditions are regularly reported. However, to prove their applicability in clinics, large multi-center multi-national studies need to be undertaken; and these will result in enormous amount of data. A parallel effort to develop analytical methods, including user-friendly software that can quickly pre-process data and subject them to required multivariate analysis is warranted in order to obtain results in real time. This study reports a MATLAB based script that can automatically import data, preprocess spectra— interpolation, derivatives, normalization, and then carry out Principal Component Analysis (PCA) followed by Linear Discriminant Analysis (LDA) of the first 10 PCs; all with a single click. The software has been verified on data obtained from cell lines, animal models, and in vivo patient datasets, and gives results comparable to Minitab 16 software. The software can be used to import variety of file extensions, asc, .txt., .xls, and many others. Options to ignore noisy data, plot all possible graphs with PCA factors 1 to 5, and save loading factors, confusion matrices and other parameters are also present. The software can provide results for a dataset of 300 spectra within 0.01 s. We believe that the software will be vital not only in clinical trials using vibrational spectroscopic data, but also to obtain rapid results when these tools get translated into clinics.

  8. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    International Nuclear Information System (INIS)

    Tomin, Vladimir I.; Ushakou, Dzmitryi V.

    2015-01-01

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  9. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  10. Comparative study on fluorescence spectra of Chinese medicine north and south isatis root granules

    Science.gov (United States)

    Liang, Lan; He, Qing; Chen, Zhenqiang; Zhu, Siqi

    2016-03-01

    Since the spectral imaging technology emerged, it has gained a lot of application achievements in the military field, precision agriculture and biomedical science. When the fluorescence spectrum imaging first applied to the detection of the feature resource of Chinese herbal medicine, the characteristics of holistic and ambiguity made it a new approach to the traditional Chinese medicine testing. In this paper, we applied this method to study the Chinese medicine north and south isatis root granules by comparing their fluorescence spectra. Using cluster analysis, the results showed that the north and south Banlangen can not be divided by ascription. And these indicate that there is a large difference in the quality of Banlangen granules on the market, and fluorescence spectrum imaging method can be used in monitoring the quality of radix isatidis granules.

  11. Raman vibrational spectra of thymol blue dyed polyvinyl alcohol (PVA) film dosimeters

    International Nuclear Information System (INIS)

    Lepit, A.; Saion, E.B.; Susilawati; Doyan, A.; Wan Yusoff, W.M.D.

    2002-01-01

    Radiation-sensitive dyed polyvinyl alcohol (PVA) film indicators containing chloral hydrate and acid-sensitive thymol blue dye have been studied for routine food irradiation dosimeters. The free standing dyed film dosimeters of different chloral hydrate concentrations (0.1, 0.5, 1.0, 2.0 and 2.5 g) were irradiated with the absorbed dose ranges from 1 kGy to 12 kGy using gamma rays from Co-60 teletherapy. Upon exposure the dosimeters undergo chemical change and become more acidic, resulting in colour change from yellow to red at the critical doses depending on the chloral hydrate concentrations. The radiation-induced change in colour was analysed using UV-Vis spectrometer that the absorption spectra produced two maximal of the visible bands peaking at 445 nm for low doses and 554 nm for high doses. Spectra of inelastic Raman scattering photons corresponding to Raman shift frequency of unirradiated and irradiated films were measured using a dispersive Raman spectrometer. The spectral intensity of C=C, C-0 and S-H molecular vibration peaks for their respective Raman shifts were studied which provide the dose response to the change of dye molecular structure of the dosimeters. (Author)

  12. Signatures in vibrational and UV-visible absorption spectra for identifying cyclic hydrocarbons by graphene fragments.

    Science.gov (United States)

    Meng, Yan; Wu, Qi; Chen, Lei; Wangmo, Sonam; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin; Ding, Dajun; Niehaus, Thomas A; Frauenheim, Thomas

    2013-12-21

    To promote possible applications of graphene in molecular identification based on stacking effects, in particular in recognizing aromatic amino acids and even sequencing nucleobases in life sciences, we comprehensively study the interaction between graphene segments and different cyclic organic hydrocarbons including benzene (C6H6), cyclohexane (C6H12), benzyne (C6H4), cyclohexene (C6H10), 1,3-cyclohexadiene (C6H8(1)) and 1,4-cyclohexadiene (C6H8(2)), using the density-functional tight-binding (DFTB) method. Interestingly, we find obviously different characteristics in Raman vibrational and ultraviolet visible absorption spectra of the small molecules adsorbed on the graphene sheet. Specifically, we find that both spectra involve clearly different characteristic peaks, belonging to the different small molecules upon adsorption, with the ones of ionized molecules being more substantial. Further analysis shows that the adsorptions are almost all due to the presence of dispersion energy in neutral cases and involve charge transfer from the graphene to the small molecules. In contrast, the main binding force in the ionic adsorption systems is the electronic interaction. The results present clear signatures that can be used to recognize different kinds of aromatic hydrocarbon rings on graphene sheets. We expect that our findings will be helpful for designing molecular recognition devices using graphene.

  13. Vibrational spectra and boson-like excitations in different amorphous forms of ice

    International Nuclear Information System (INIS)

    Kolesnikov, A.I.; Li, J.C.; Uffindell, C.H.

    1999-01-01

    Complete text of publication follows. Glasses are very interesting objects in the physics of condensed matter, with many universal properties, such as low-energy excitations (LEE) coexisting with the sound waves and giving an excess of vibrational modes with respect to the crystalline spectrum (the so called 'boson' peak) in Raman and inelastic neutron scattering (INS). Recently it was discovered that films of hydrogenated amorphous silicon do not show such LEE, whereas films of amorphous silicon do [1]. Also, the resonant absorption by two-level systems was observed for the high-density amorphous (hda) ice but not for the low-density amorphous (lda) ice in the far infrared spectra [2]. Thus, the nature of these near universal LEE becomes rather puzzling. This report presents the results of INS studies for hda and lda ice produced by high-pressure treatment and for vapor-deposited lda ice. Clear LEE were observed in the spectra for hda and deposited lda ice unlike their crystalline analogues. (author)

  14. Multilinear analysis of Time-Resolved Laser-Induced Fluorescence Spectra of U(VI containing natural water samples

    Directory of Open Access Journals (Sweden)

    Višňák Jakub

    2017-01-01

    Full Text Available Natural waters’ uranium level monitoring is of great importance for health and environmental protection. One possible detection method is the Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS, which offers the possibility to distinguish different uranium species. The analytical identification of aqueous uranium species in natural water samples is of distinct importance since individual species differ significantly in sorption properties and mobility in the environment. Samples originate from former uranium mine sites and have been provided by Wismut GmbH, Germany. They have been characterized by total elemental concentrations and TRLFS spectra. Uranium in the samples is supposed to be in form of uranyl(VI complexes mostly with carbonate (CO32− and bicarbonate (HCO3− and to lesser extend with sulphate (SO42− , arsenate (AsO43− , hydroxo (OH− , nitrate (NO3− and other ligands. Presence of alkaline earth metal dications (M = Ca2+ , Mg2+ , Sr2+ will cause most of uranyl to prefer ternary complex species, e.g. Mn(UO2(CO332n-4 (n ∊ {1; 2}. From species quenching the luminescence, Cl− and Fe2+ should be mentioned. Measurement has been done under cryogenic conditions to increase the luminescence signal. Data analysis has been based on Singular Value Decomposition and monoexponential fit of corresponding loadings (for separate TRLFS spectra, the “Factor analysis of Time Series” (FATS method and Parallel Factor Analysis (PARAFAC, all data analysed simultaneously. From individual component spectra, excitation energies T00, uranyl symmetric mode vibrational frequencies ωgs and excitation driven U-Oyl bond elongation ΔR have been determined and compared with quasirelativistic (TDDFT/B3LYP theoretical predictions to cross -check experimental data interpretation.

  15. Multilinear analysis of Time-Resolved Laser-Induced Fluorescence Spectra of U(VI) containing natural water samples

    Science.gov (United States)

    Višňák, Jakub; Steudtner, Robin; Kassahun, Andrea; Hoth, Nils

    2017-09-01

    Natural waters' uranium level monitoring is of great importance for health and environmental protection. One possible detection method is the Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), which offers the possibility to distinguish different uranium species. The analytical identification of aqueous uranium species in natural water samples is of distinct importance since individual species differ significantly in sorption properties and mobility in the environment. Samples originate from former uranium mine sites and have been provided by Wismut GmbH, Germany. They have been characterized by total elemental concentrations and TRLFS spectra. Uranium in the samples is supposed to be in form of uranyl(VI) complexes mostly with carbonate (CO32- ) and bicarbonate (HCO3- ) and to lesser extend with sulphate (SO42- ), arsenate (AsO43- ), hydroxo (OH- ), nitrate (NO3- ) and other ligands. Presence of alkaline earth metal dications (M = Ca2+ , Mg2+ , Sr2+ ) will cause most of uranyl to prefer ternary complex species, e.g. Mn(UO2)(CO3)32n-4 (n ɛ {1; 2}). From species quenching the luminescence, Cl- and Fe2+ should be mentioned. Measurement has been done under cryogenic conditions to increase the luminescence signal. Data analysis has been based on Singular Value Decomposition and monoexponential fit of corresponding loadings (for separate TRLFS spectra, the "Factor analysis of Time Series" (FATS) method) and Parallel Factor Analysis (PARAFAC, all data analysed simultaneously). From individual component spectra, excitation energies T00, uranyl symmetric mode vibrational frequencies ωgs and excitation driven U-Oyl bond elongation ΔR have been determined and compared with quasirelativistic (TD)DFT/B3LYP theoretical predictions to cross -check experimental data interpretation. Note to the reader: Several errors have been produced in the initial version of this article. This new version published on 23 October 2017 contains all the corrections.

  16. Control method for multi-input multi-output non-Gaussian random vibration test with cross spectra consideration

    Directory of Open Access Journals (Sweden)

    Ronghui ZHENG

    2017-12-01

    Full Text Available A control method for Multi-Input Multi-Output (MIMO non-Gaussian random vibration test with cross spectra consideration is proposed in the paper. The aim of the proposed control method is to replicate the specified references composed of auto spectral densities, cross spectral densities and kurtoses on the test article in the laboratory. It is found that the cross spectral densities will bring intractable coupling problems and induce difficulty for the control of the multi-output kurtoses. Hence, a sequential phase modification method is put forward to solve the coupling problems in multi-input multi-output non-Gaussian random vibration test. To achieve the specified responses, an improved zero memory nonlinear transformation is utilized first to modify the Fourier phases of the signals with sequential phase modification method to obtain one frame reference response signals which satisfy the reference spectra and reference kurtoses. Then, an inverse system method is used in frequency domain to obtain the continuous stationary drive signals. At the same time, the matrix power control algorithm is utilized to control the spectra and kurtoses of the response signals further. At the end of the paper, a simulation example with a cantilever beam and a vibration shaker test are implemented and the results support the proposed method very well. Keywords: Cross spectra, Kurtosis control, Multi-input multi-output, Non-Gaussian, Random vibration test

  17. Assessment of electron propagator methods for the simulation of vibrationally-resolved valence and core photoionization spectra

    Science.gov (United States)

    Baiardi, A.; Paoloni, L.; Barone, V.; Zakrzewski, V.G.; Ortiz, J.V.

    2017-01-01

    The analysis of photoelectron spectra is usually facilitated by quantum mechanical simulations. Due to the recent improvement of experimental techniques, the resolution of experimental spectra is rapidly increasing, and the inclusion of vibrational effects is usually mandatory to obtain a reliable reproduction of the spectra. With the aim of defining a robust computational protocol, a general time-independent formulation to compute different kinds of vibrationally-resolved electronic spectra has been generalized to support also photoelectron spectroscopy. The electronic structure data underlying the simulation are computed using different electron propagator approaches. In addition to the more standard approaches, a new and robust implementation of the second-order self-energy approximation of the electron propagator based on a transition operator reference (TOEP2) is presented. To validate our implementation, a series of molecules has been used as test cases. The result of the simulations shows that, for ultraviolet photoionization spectra, the more accurate non-diagonal approaches are needed to obtain a reliable reproduction of vertical ionization energies, but diagonal approaches are sufficient for energy gradients and pole strengths. For X-ray photoelectron spectroscopy, the TOEP2 approach, besides being more efficient, is also the most accurate in the reproduction of both vertical ionization energies and vibrationally-resolved bandshapes. PMID:28521087

  18. Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species

    International Nuclear Information System (INIS)

    Pirali, O.; Gruet, S.; Kisiel, Z.; Goubet, M.; Martin-Drumel, M. A.; Cuisset, A.; Hindle, F.; Mouret, G.

    2015-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution study of the three lowest vibrational states of quinoline C 9 H 7 N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν 45 and ν 44 vibrational modes (located at about 168 cm −1 and 178 cm −1 , respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations

  19. Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species

    Science.gov (United States)

    Pirali, O.; Kisiel, Z.; Goubet, M.; Gruet, S.; Martin-Drumel, M. A.; Cuisset, A.; Hindle, F.; Mouret, G.

    2015-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution study of the three lowest vibrational states of quinoline C9H7N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν45 and ν44 vibrational modes (located at about 168 cm-1 and 178 cm-1, respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations.

  20. IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part II

    International Nuclear Information System (INIS)

    Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Csaszar, Attila G.; Daumont, Ludovic; Gamache, Robert R.; Hodges, Joseph T.; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Toth, Robert A.; Vandaele, Ann Carine; Zobov, Nikolai F.; Fally, Sophie; Fazliev, Alexander Z.; Furtenbacher, Tibor; Gordon, Iouli E.; Hu, Shui-Ming

    2010-01-01

    This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD 16 O, HD 17 O, and HD 18 O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm -1 for HD 16 O, HD 17 O, and HD 18 O, respectively. For HD 16 O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD 17 O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD 18 O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD 16 O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W-DIS, where they can easily be retrieved. In addition, the transition and energy level information for H 2 17 O and H 2 18 O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated.

  1. A support vector machine approach to the automatic identification of fluorescence spectra emitted by biological agents

    Science.gov (United States)

    Gelfusa, M.; Murari, A.; Lungaroni, M.; Malizia, A.; Parracino, S.; Peluso, E.; Cenciarelli, O.; Carestia, M.; Pizzoferrato, R.; Vega, J.; Gaudio, P.

    2016-10-01

    Two of the major new concerns of modern societies are biosecurity and biosafety. Several biological agents (BAs) such as toxins, bacteria, viruses, fungi and parasites are able to cause damage to living systems either humans, animals or plants. Optical techniques, in particular LIght Detection And Ranging (LIDAR), based on the transmission of laser pulses and analysis of the return signals, can be successfully applied to monitoring the release of biological agents into the atmosphere. It is well known that most of biological agents tend to emit specific fluorescence spectra, which in principle allow their detection and identification, if excited by light of the appropriate wavelength. For these reasons, the detection of the UVLight Induced Fluorescence (UV-LIF) emitted by BAs is particularly promising. On the other hand, the stand-off detection of BAs poses a series of challenging issues; one of the most severe is the automatic discrimination between various agents which emit very similar fluorescence spectra. In this paper, a new data analysis method, based on a combination of advanced filtering techniques and Support Vector Machines, is described. The proposed approach covers all the aspects of the data analysis process, from filtering and denoising to automatic recognition of the agents. A systematic series of numerical tests has been performed to assess the potential and limits of the proposed methodology. The first investigations of experimental data have already given very encouraging results.

  2. Fluorescence Imaging of Rotational and Vibrational Temperature in a Shock Tunnel Nozzle Flow

    Science.gov (United States)

    Palma, Philip C.; Danehy, Paul M.; Houwing, A. F. P.

    2003-01-01

    Two-dimensional rotational and vibrational temperature measurements were made at the nozzle exit of a free-piston shock tunnel using planar laser-induced fluorescence. The Mach 7 flow consisted predominantly of nitrogen with a trace quantity of nitric oxide. Nitric oxide was employed as the probe species and was excited at 225 nm. Nonuniformities in the distribution of nitric oxide in the test gas were observed and were concluded to be due to contamination of the test gas by driver gas or cold test gas.The nozzle-exit rotational temperature was measured and is in reasonable agreement with computational modeling. Nonlinearities in the detection system were responsible for systematic errors in the measurements. The vibrational temperature was measured to be constant with distance from the nozzle exit, indicating it had frozen during the nozzle expansion.

  3. The Utilization of Low Frequency Raman Spectra of Gases for the Study of Molecules with Large Amplitude Vibration

    Institute of Scientific and Technical Information of China (English)

    James R. Durig; Sarah Xiao-hua Zhou; Joshua Klaassen; Arindam Ganguly

    2009-01-01

    The utilization of the Raman spectra of the low frequency bending mode for three quasi-linear molecules, disiloxane, (SiH3)2 O; methylisocyanate, CH3NCO; and dimethy lisocyanate, (CH3)2SiHNCO for observing the low frequency anharmonic bending vibration is demonstrated which is superior to the corresponding far infrared spectra. From the observed frequencies from the Raman spectra the potential function governing the heavy atom motion to linearity has been obtained from which the barrier has been determined. These experimental values are compared to the ab ini-tio predicted values. Also low frequency Raman spectra of the ring puckering vibration of chlorocy-clobutane, c-C4H7Cl, bromocyclobutane, c-C4H7Br, and aminocyclobutane, c-C4H7NH2, have been utilized to obtain the potential function governing the ring inversion for these molecules. The deter-mined barriers to planarity are compared to those obtained from MP2 (full) ab initio and density functional theory B3LYP calculations by utilizing a variety of basis sets. For all of these studies it is shown that the Raman spectra are superior to the infrared spectra for determining the frequencies of the excited state transitions.

  4. [Identification of spill oil species based on low concentration synchronous fluorescence spectra and RBF neural network].

    Science.gov (United States)

    Liu, Qian-qian; Wang, Chun-yan; Shi, Xiao-feng; Li, Wen-dong; Luan, Xiao-ning; Hou, Shi-lin; Zhang, Jin-liang; Zheng, Rong-er

    2012-04-01

    In this paper, a new method was developed to differentiate the spill oil samples. The synchronous fluorescence spectra in the lower nonlinear concentration range of 10(-2) - 10(-1) g x L(-1) were collected to get training data base. Radial basis function artificial neural network (RBF-ANN) was used to identify the samples sets, along with principal component analysis (PCA) as the feature extraction method. The recognition rate of the closely-related oil source samples is 92%. All the results demonstrated that the proposed method could identify the crude oil samples effectively by just one synchronous spectrum of the spill oil sample. The method was supposed to be very suitable to the real-time spill oil identification, and can also be easily applied to the oil logging and the analysis of other multi-PAHs or multi-fluorescent mixtures.

  5. Stabilizing the PARAFAC decomposition of fluorescence spectra by insertion of zeros outside the data area

    DEFF Research Database (Denmark)

    Thygesen, Lisbeth Garbrecht; Rinnan, Åsmund; Barsberg, Søren

    2004-01-01

    landscape, several light-scatter effects are usually present, and often the part of the landscape containing information on the chemical and/or physical characteristics of the sample is surrounded by two Rayleigh scatter lines. When such landscapes are decomposed using parallel factor analysis (PARAFAC......), the scatter effects may have detrimental effects on the resolved spectra, especially if the peaks from the analytes lie close to or on the Rayleigh scatter lines. Normally, all values close to and outside the Rayleigh scatter lines are set to missing values before decomposing the fluorescence landscapes...... by PARAFAC. In this paper, we introduce a novel pretreatment method applicable for two-dimensional fluorescence landscapes, where instead of inserting only missing values a mixture of zeros and missing values are inserted close to and outside the Rayleigh scatter lines. It is shown that, by the use...

  6. Resonance fluorescence spectra of three-level atoms in a squeezed vacuum

    International Nuclear Information System (INIS)

    Ferguson, M.R.; Ficek, Z.; Dalton, B.J.

    1996-01-01

    The fluorescence field from one of the two allowed transitions in a three-level atom can sense squeezed fluctuations of a vacuum field coupled to the other transition. We examine the fluorescence spectra of strongly driven three-level atoms in Λ, V, and cascade configurations in which one of the two one-photon transitions is coupled to a finite-bandwidth squeezed vacuum field, when the bandwidth is much smaller than the difference in the atomic transition frequencies, though much larger than atomic decay rates and Rabi frequencies of the driving fields. The driving fields are on one-photon resonance, and the squeezed vacuum field is generated by a degenerate parameter oscillator. Details are only given for the Λ configuration. The extension to the V and cascade configurations is straightforward. We find that in all configurations the fluorescence spectra of the transition not coupled to the squeezed vacuum field are composed of five lines, one central and two pairs of sidebands, with intensities and widths strongly influenced by the squeezed vacuum field. However, only the central component and the outer sidebands exhibit a dependence on the squeezing phase. We also examine the fluorescence spectrum for the cascade configuration with a squeezed vacuum field on resonance with the two-photon transition between the ground and the most excited states and now generated by a nondegenerate parametric oscillator. In this case, where the squeezed vacuum field can be made coupled to both transitions, all spectral lines depend on the squeezing phase. The spectral features are explained in terms of the dressed-atom model of the system. We show that the coherent mixing of the atomic states by the strong driving fields modifies transition rates between the dressed states, which results in the selective phase dependence of the spectral features. copyright 1996 The American Physical Society

  7. Application of direct peak analysis to energy dispersive x-ray fluorescence spectra

    International Nuclear Information System (INIS)

    Nielson, K.K.

    1977-07-01

    A modified Covell method for direct peak analysis has been applied to energy dispersive x-ray fluorescence spectra. The method is background independent and is well-suited to computerized data reduction. It provides acceptable precision, minimizes errors from instrumental gain shift, and permits peak overlap correction. Peak overlap errors exhibit both positive and negative nodes as a function of peak separation distance, and are corrected using concentration ratios determined from thin, single-element standards. Peak precisions and overlaps are evaluated as a function of window width to aid in width selection. Least-square polynomial smoothing prior to peak analysis significantly improves peak area precisions without significantly affecting their accuracies

  8. Vibrational spectra of nanowires measured using laser doppler vibrometry and STM studies of epitaxial graphene : an LDRD fellowship report.

    Energy Technology Data Exchange (ETDEWEB)

    Biedermann, Laura Butler

    2009-09-01

    A few of the many applications for nanowires are high-aspect ratio conductive atomic force microscope (AFM) cantilever tips, force and mass sensors, and high-frequency resonators. Reliable estimates for the elastic modulus of nanowires and the quality factor of their oscillations are of interest to help enable these applications. Furthermore, a real-time, non-destructive technique to measure the vibrational spectra of nanowires will help enable sensor applications based on nanowires and the use of nanowires as AFM cantilevers (rather than as tips for AFM cantilevers). Laser Doppler vibrometry is used to measure the vibration spectra of individual cantilevered nanowires, specifically multiwalled carbon nanotubes (MWNTs) and silver gallium nanoneedles. Since the entire vibration spectrum is measured with high frequency resolution (100 Hz for a 10 MHz frequency scan), the resonant frequencies and quality factors of the nanowires are accurately determined. Using Euler-Bernoulli beam theory, the elastic modulus and spring constant can be calculated from the resonance frequencies of the oscillation spectrum and the dimensions of the nanowires, which are obtained from parallel SEM studies. Because the diameters of the nanowires studied are smaller than the wavelength of the vibrometer's laser, Mie scattering is used to estimate the lower diameter limit for nanowires whose vibration can be measured in this way. The techniques developed in this thesis can be used to measure the vibrational spectra of any suspended nanowire with high frequency resolution Two different nanowires were measured - MWNTs and Ag{sub 2}Ga nanoneedles. Measurements of the thermal vibration spectra of MWNTs under ambient conditions showed that the elastic modulus, E, of plasma-enhanced chemical vapor deposition (PECVD) MWNTs is 37 {+-} 26 GPa, well within the range of E previously reported for CVD-grown MWNTs. Since the Ag{sub 2}Ga nanoneedles have a greater optical scattering efficiency than

  9. Isotopically decoupled vibrational spectra and proton exchange rates for crystalline NH3 and ammonia hydrate

    Science.gov (United States)

    Thornton, Cynthia; Khatkale, M. S.; Devlin, J. Paul

    1981-12-01

    Codeposits of NH3 with ND3 or D2O have been prepared at liquid nitrogen temperatures in the absence of proton exchange. Vibrational data for the anhydrous cubic crystalline ammonia, containing isolated NH3 or ND3, confirm that, relative to water ice, intermolecular coupling in ammonia ice exerts a relatively minor influence on the infrared and Raman spectra. Nevertheless, sizeable decoupling shifts, particularly for ν1, have been observed and attributed to a combination of factors including correlation field and Fermi resonance effects. The Raman polarization data has also affirmed long standing assignments of ν1 and ν3 for ammonia ice. Warming of the ammonia thin films resulted in limited isotopic scrambling at 130 K, apparently possible only through the agency of trace concentrations of water. The vibrational coupling pattern for the resultant NHD2 and NH2D molecules suggest that proton (deuteron) migration away from the exchange centers is impossible at temperatures up to 150 K. By contrast, isotopic scrambling was rapid and complete at 140 K for amorphous ammonia hydrate films (˜35% NH3, ˜65% D2O) which were also prepared without exchange at ˜90 K. The proton (deuteron) exchange rate is much greater for the amorphous ammonia hydrate at 140 K than for pure water ice. Such exchange requires both ion-pair defect formation and proton mobility. Since the NH3 suppresses the H3O+ concentration via formation of NH+4, a suppression the likes of which has been shown to stop proton exchange in water ice, the evidence strongly suggests that NH4+ in ammonia, like H3O+ in water, is an effective proton transfer agent, probably acting through a tunneling mechanism (i.e., H3N+-HṡṡṡNH3→H3NṡṡṡH-N+H3 etc.) to render the proton mobile in the ammonia hydrate. This mobility combined with the greater NH4+ concentration, relative to the H3O+ concentration in H2O ice Ic, results in isotopic scrambling at the reduced temperature.

  10. Determination by vibrational spectra of the strength and the bond length of atoms U and O in uranyl complexes

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1996-01-01

    The vibrational spectra of different uranyl compounds were studied. The wave number was related to the harmonic oscillator model and to the mathematical expression of Badger as modified by Jones, to determine the strength and the bond length of atoms U and O in UO 2 2+ . A mathematical simplification develop by us is proposed and its results compared with values obtained by other methods. (Author)

  11. Photosynthetic complex LH2 – Absorption and steady state fluorescence spectra

    International Nuclear Information System (INIS)

    Zapletal, David; Heřman, Pavel

    2014-01-01

    Nowadays, much effort is devoted to the study of photosynthesis which could be the basis for an ideal energy source in the future. To be able to create such an energy source – an artificial photosynthetic complex, the first step is a detailed understanding of the function of photosynthetic complexes in living organisms. Photosynthesis starts with the absorption of a solar photon by one of the LH (light-harvesting) pigment–protein complexes and transferring the excitation energy to the reaction center where a charge separation is initiated. The geometric structure of some LH complexes is known in great detail, e.g. for the LH2 complexes of purple bacteria. For understanding of photosynthesis first stage efficiency, it is necessary to study especially optical properties of LH complexes. In this paper we present simulated absorption and steady-state fluorescence spectra for ring molecular system within full Hamiltonian model. Such system can model bacteriochlorophyll ring of peripheral light-harvesting complex LH2 from purple bacterium Rhodopseudomonas acidophila (Rhodoblastus acidophilus). Dynamic disorder (coupling with phonon bath) simultaneously with uncorrelated static disorder (transfer integral fluctuations) is used in our present simulations. We compare and discuss our new results with our previously published ones and of course with experimental data. - Highlights: • We model absorption and steady state fluorescence spectra for B850 ring from LH2. • Fluctuations of environment is modelled by static and dynamic disorder. • Full Hamiltonian model is compared with the nearest neighbour approximation one. • Simulated fluorescence spectrum is compared with experimental data

  12. Improved Savitzky-Golay-method-based fluorescence subtraction algorithm for rapid recovery of Raman spectra.

    Science.gov (United States)

    Chen, Kun; Zhang, Hongyuan; Wei, Haoyun; Li, Yan

    2014-08-20

    In this paper, we propose an improved subtraction algorithm for rapid recovery of Raman spectra that can substantially reduce the computation time. This algorithm is based on an improved Savitzky-Golay (SG) iterative smoothing method, which involves two key novel approaches: (a) the use of the Gauss-Seidel method and (b) the introduction of a relaxation factor into the iterative procedure. By applying a novel successive relaxation (SG-SR) iterative method to the relaxation factor, additional improvement in the convergence speed over the standard Savitzky-Golay procedure is realized. The proposed improved algorithm (the RIA-SG-SR algorithm), which uses SG-SR-based iteration instead of Savitzky-Golay iteration, has been optimized and validated with a mathematically simulated Raman spectrum, as well as experimentally measured Raman spectra from non-biological and biological samples. The method results in a significant reduction in computing cost while yielding consistent rejection of fluorescence and noise for spectra with low signal-to-fluorescence ratios and varied baselines. In the simulation, RIA-SG-SR achieved 1 order of magnitude improvement in iteration number and 2 orders of magnitude improvement in computation time compared with the range-independent background-subtraction algorithm (RIA). Furthermore the computation time of the experimentally measured raw Raman spectrum processing from skin tissue decreased from 6.72 to 0.094 s. In general, the processing of the SG-SR method can be conducted within dozens of milliseconds, which can provide a real-time procedure in practical situations.

  13. Crystal structure, vibrational spectra and DFT studies of hydrogen bonded 1,2,4-triazolium hydrogenselenate

    Science.gov (United States)

    Arjunan, V.; Thirunarayanan, S.; Marchewka, M. K.; Mohan, S.

    2017-10-01

    The new hydrogen bonded molecular complex 1,2,4-triazolium hydrogenselenate (THS) is prepared by the reaction of 1H-1,2,4-triazole and selenic acid. This complex is stabilised by N-H⋯O and C-H⋯O hydrogen bonding and electrostatic attractive forces between 1H and 1,2,4-triazolium cations and hydrogen selenate anions. The XRD studies revealed that intermolecular proton transfer occur from selenic acid to 1H-1,2,4-triazole molecule, results in the formation of 1,2,4-triazolium hydrogenselenate which contains 1,2,4-triazolium cations and hydrogenselenate anions. The molecular structure of THS crystal has also been optimised by using Density Functional Theory (DFT) using B3LYP/cc-pVTZ and B3LYP/6-311++G** methods in order to find the whole characteristics of the molecular complex. The theoretical structural parameters such as bond length, bond angle and dihedral angle determined by DFT methods are well agreed with the XRD parameters. The atomic charges and thermodynamic properties are also calculated and analysed. The energies of frontier molecular orbitals HOMO, LUMO, HOMO-1, LUMO+1 and LUMO-HUMO energy gap are calculated to understand the kinetic stability and chemical reactivity of the molecular complex. The natural bond orbital analysis (NBO) has been performed in order to study the intramolecular bonding interactions and delocalisation of electrons. These intra molecular charge transfer may induce biological activities such as antimicrobials, antiinflammatory, antifungal etc. The complete vibrational assignments of THS have been performed by using FT-IR and FT-Raman spectra.

  14. Li{sub 4}Ba[BN{sub 2}]{sub 2} - structure and vibrational spectra

    Energy Technology Data Exchange (ETDEWEB)

    Seidel, Stefan; Rodewald, Ute C.; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Somer, Mehmet; Kiraz, Kamil [Chemistry Department, Koc University, Sariyer-Istanbul (Turkey)

    2017-12-13

    The nitridoborate Li{sub 4}Ba[BN{sub 2}]{sub 2} was synthesized from a 4:1 molar ratio of Li{sub 3}[BN]{sub 2} and Ba{sub 3}[BN{sub 2}]{sub 2} in an arc-welded niobium ampoule at a maximum annealing temperature of 1173 K. The structure was refined from single-crystal X-ray diffractometer data: new type, P1, a = 533.9(2), b = 585.0(3), c = 860.6(4) pm, α = 80.72(3), β = 73.84(6), γ = 89.87(4) , wR{sub 2} = 0.1196, 1429 F{sup 2} values, 50 variables. The Li{sub 4}Ba[BN{sub 2}]{sub 2} structure contains two crystallographically independent [BN{sub 2}]{sup 3-} units with 134 pm B-N distance, which are slightly bent: 178 for N2-B1-N1 and 175 for N4-B2-N3. Due to the high lithium content both [BN{sub 2}]{sup 3-} units have a strongly distorted coordination by 8Li{sup +} + 3Ba{sup 2+}. The four crystallographically independent lithium cations show distorted tetrahedral coordination by [BN{sub 2}]{sup 3-} units with Li-N distances ranging from 195 to 247 pm. IR and Raman spectra show the typical vibrations of the [BN{sub 2}] unit along with a well-resolved splitting of the ν({sup 10}B) and ν({sup 11}B) frequencies. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species

    Energy Technology Data Exchange (ETDEWEB)

    Pirali, O.; Gruet, S. [AILES Beamline, Synchrotron SOLEIL, l’Orme des Merisiers, Saint-Aubin, 91192 Gif-sur-Yvette cedex (France); Institut des Sciences Moléculaires d’Orsay, UMR8214 CNRS – Université Paris-Sud, Bât. 210, 91405 Orsay cedex (France); Kisiel, Z. [Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland); Goubet, M. [Laboratoire de Physique des Lasers, Atomes et Molécules, UMR 8523 CNRS - Université Lille 1, Bâtiment P5, F-59655 Villeneuve d’Ascq Cedex (France); Martin-Drumel, M. A.; Cuisset, A.; Hindle, F.; Mouret, G. [Laboratoire de Physico-Chimie de l’Atmosphère, EA-4493, Université du Littoral – Côte d’Opale, 59140 Dunkerque (France)

    2015-03-14

    Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution study of the three lowest vibrational states of quinoline C{sub 9}H{sub 7}N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν{sub 45} and ν{sub 44} vibrational modes (located at about 168 cm{sup −1} and 178 cm{sup −1}, respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations.

  16. Variable selection based on clustering analysis for improvement of polyphenols prediction in green tea using synchronous fluorescence spectra

    Science.gov (United States)

    Shan, Jiajia; Wang, Xue; Zhou, Hao; Han, Shuqing; Riza, Dimas Firmanda Al; Kondo, Naoshi

    2018-04-01

    Synchronous fluorescence spectra, combined with multivariate analysis were used to predict flavonoids content in green tea rapidly and nondestructively. This paper presented a new and efficient spectral intervals selection method called clustering based partial least square (CL-PLS), which selected informative wavelengths by combining clustering concept and partial least square (PLS) methods to improve models’ performance by synchronous fluorescence spectra. The fluorescence spectra of tea samples were obtained and k-means and kohonen-self organizing map clustering algorithms were carried out to cluster full spectra into several clusters, and sub-PLS regression model was developed on each cluster. Finally, CL-PLS models consisting of gradually selected clusters were built. Correlation coefficient (R) was used to evaluate the effect on prediction performance of PLS models. In addition, variable influence on projection partial least square (VIP-PLS), selectivity ratio partial least square (SR-PLS), interval partial least square (iPLS) models and full spectra PLS model were investigated and the results were compared. The results showed that CL-PLS presented the best result for flavonoids prediction using synchronous fluorescence spectra.

  17. FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular conformational analysis of 2,5-di-tert-butyl-hydroquinone

    Science.gov (United States)

    Subramanian, N.; Sundaraganesan, N.; Dereli, Ö.; Türkkan, E.

    2011-12-01

    The purpose of finding conformer among six different possible conformers of 2,5-di-tert-butyl-hydroquinone (DTBHQ), its equilibrium geometry and harmonic wavenumbers were calculated by the B3LYP/6-31G(d,p) method. The infrared and Raman spectra of DTBHQ were recorded in the region 400-4000 cm -1 and 50-3500 cm -1, respectively. In addition, the IR spectra in CCl 4 at various concentrations of DTBHQ are also recorded. The computed vibrational wavenumbers were compared with the IR and Raman experimental data. Computational calculations at B3LYP level with two different basis sets 6-31G(d,p) and 6-311++G(d,p) are also employed in the study of the possible conformer of DTBHQ. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA 4 program. The general agreement between the observed and calculated frequencies was established.

  18. Vibrational dynamics of adsorbed molecules under conditions of photodesorption: Pump-probe SFG spectra of CO/Pt(111)

    Science.gov (United States)

    Fournier, Frédéric; Zheng, Wanquan; Carrez, Serge; Dubost, Henri; Bourguignon, Bernard

    2004-09-01

    Interaction of CO adsorbed on Pt(111) with electrons and phonons is studied experimentally by means of a pump-probe experiment where CO is probed by IR+visible sum frequency generation under a pump laser intensity that allows photodesorption. Vibrational spectra of CO internal stretch are obtained as a function of pump-probe delay. A two-temperature and anharmonic coupling model is used to extract from the spectra the real time variations of CO peak frequency and dephasing time. The main conclusions are the following: (i) The CO stretch is perturbed by two low-frequency modes, assigned to frustrated rotation and frustrated translation. (ii) The frustrated rotation is directly coupled to electrons photoexcited in Pt(111) by the pump laser. (iii) There is no evidence of Pt-CO stretch excitation in the spectra. The implications for the photodesorption dynamics are discussed.

  19. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    International Nuclear Information System (INIS)

    Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

    2010-01-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

  20. Large Amplitude Motions in Polyatomic Molecule Spectra: Intramolecular Vibrational Redistribution and Isomerization

    National Research Council Canada - National Science Library

    Field, Robert

    1997-01-01

    Through Stimulated Emission Pumping (SEP) studies of highly excited vibrational levels of the electronic ground state of HCP, the spectroscopic signatures of bond breaking isomer/atom (HCP right arrow HPC...

  1. Experimental and Theoretical Vibrational Spectra of Sideridiol Isolated from Sideritis Species

    Science.gov (United States)

    Kilic, Turgut; Sagir, Züleyha Ozer; Carikci, Sema; Azizoğlu, Akın

    2017-12-01

    Sideridiol ( ent-7α,18β-dihydroxykaur-15-ene) one of the ent-kaurene diterpenoid, is isolated from the genus Sideritis L. belongs to the family of Lamiaceae. The vibrational frequencies of sideridiol in the ground state have been calculated using the Density Functional Theory (DFT) method with the 6-31G( d) and 6 31+G( d, p) basis sets. The calculated vibrational frequencies have been compared with that of obtained experimental IR spectrum.

  2. Regio-Regular Oligo and Poly(3-hexyl thiophene): Precise Structural Markers from the Vibrational Spectra of Oligomer Single Crystals.

    KAUST Repository

    Brambilla, Luigi

    2014-10-14

    © 2014 American Chemical Society. In this work, we report a comparative analysis of the infrared and Raman spectra of octa(3-hexylthiophene) (3HT)8, trideca(3-hexylthiophene) (3HT)13, and poly(3-hexylthiophene) P3HT recorded in various phases, namely, amorphous, semicrystalline, polycrystalline and single crystal. We have based our analysis on the spectra of the (3HT)8 single crystal (whose structure has been determined by selected area electron diffraction) taken as reference and on the results of DFT calculations and molecular vibrational dynamics. New and precise spectroscopic markers of the molecular structures show the existence of three phases, namely: hairy (phase 1), ordered (phase 2), and disordered/amorphous (phase 3). Conceptually, the identified markers can be used for the molecular structure analysis of other similar systems.

  3. Vibrational spectra of water solutions of azoles from QM/MM calculations: effects of solvation.

    Science.gov (United States)

    Tanzi, Luana; Ramondo, Fabio; Guidoni, Leonardo

    2012-10-18

    Using microsolvation models and mixed quantum/classical ab initio molecular dynamics simulations, we investigate the vibrational properties of two azoles in water solution: pyrazole and oxazole. The effects of the water-azole hydrogen bonding are rationalized by an extensive comparison between structural parameters and harmonic frequencies obtained by microsolvation models. Following the effective normal-mode analysis introduced by Martinez et al. [Martinez et al., J. Chem. Phys. 2006, 125, 144106], we identify the vibrational frequencies of the solutes using the decomposition of the vibrational density of states of the gas phase and solution dynamics. The calculated shifts from gas phase to solution are fairly in agreement with the available experimental data.

  4. Molecular structure and vibrational spectra of 6-methylquinoline and 8-methylquinoline molecules by quantum mechanical methods

    International Nuclear Information System (INIS)

    Kurt, M.

    2005-01-01

    The molecular geometry and vibrational frequencies of 6-methylquinoline(6MQ) and 8-methylquinolines(8MQ) in the ground state have been calculated by using the Hartree-Fock and density functional methods (B3LYP and BLYP) with 6-31G (d) as the basis set. The optimized geometric bond lengths obtained by using B3LYP and bond angles obtained by BLYP were given corresponding experimental values of similar molecule. Comparison of the observed fundamental vibrational frequencies of these molecules and calculated results by density functional B3LYP, BLYP and Hartree-Fock methods indicates that B3LYP is superior to the scaled Hartree- Fock and BLYP approach for molecular vibrational problems

  5. An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

    Science.gov (United States)

    Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

    2018-05-01

    This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

  6. Hydrophobic radical influence on structure and vibration spectra of zwitter-ionic forms of glycine and alanine in condensed state

    International Nuclear Information System (INIS)

    Ten, G.N.; Kadrov, D.M.; Baranov, V.I.

    2014-01-01

    Structure and vibrational spectra of the zwitter-ionic forms of glycine and alanine in water solution and solid state have been calculated in the B3LYP/6-311++G(d,p) approximation. The environment influence has been taken into account by two methods: the self-consistent reaction field (SCRF) method and one of modeling the glycine and alanine complexes with molecules of water. The structure, energy and spectral properties have been determined which allow establishing an influence of the hydrophobic radical on the glycine and alanine ability to form the hydrogen bonds. It is shown by comparison with experiment that for the calculation of vibrational (IR and Raman) spectra of the zwitter-ionic forms of glycine and alanine in the condensed states they must be surrounded with three molecules of water, one of which is located between the N + H 3 and COO - ionic groups. The value of energy necessary to form the Ala complexes with water compared to Gly ones is 56.47 and 12.55 kcal/mol higher in the case of the complex formation with 1and 3 molecules of water, respectively, located between bipolar groups. (authors)

  7. Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Boda, Łukasz, E-mail: lboda@chemia.uj.edu.pl; Boczar, Marek; Gług, Maciej; Wójcik, Marek J. [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland)

    2015-11-28

    Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl–H and Cl–D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl–H and Cl–D stretching bands were performed and the results were compared with experimental spectra.

  8. Hydrogen-Bonding Network and OH Stretch Vibration of Cellulose: Comparison of Computational Modeling with Polarized IR and SFG Spectra.

    Science.gov (United States)

    Lee, Christopher M; Kubicki, James D; Fan, Bingxin; Zhong, Linghao; Jarvis, Michael C; Kim, Seong H

    2015-12-10

    Hydrogen bonds play critical roles in noncovalent directional interactions determining the crystal structure of cellulose. Although diffraction studies accurately determined the coordinates of carbon and oxygen atoms in crystalline cellulose, the structural information on hydrogen atoms involved in hydrogen-bonding is still elusive. This could be complemented by vibrational spectroscopy; but the assignment of the OH stretch peaks has been controversial. In this study, we performed calculations using density functional theory with dispersion corrections (DFT-D2) for the cellulose Iβ crystal lattices with the experimentally determined carbon and oxygen coordinates. DFT-D2 calculations revealed that the OH stretch vibrations of cellulose are highly coupled and delocalized through intra- and interchain hydrogen bonds involving all OH groups in the crystal. Additionally, molecular dynamics (MD) simulations of a single cellulose microfibril showed that the conformations of OH groups exposed at the microfibril surface are not well-defined. Comparison of the computation results with the experimentally determined IR dichroism of uniaxially aligned cellulose microfibrils and the peak positions of various cellulose crystals allowed unambiguous identification of OH stretch modes observed in the vibrational spectra of cellulose.

  9. Complicated Fermi-type vibronic resonance: Untangling of the single-site quasi-line fluorescence excitation spectra of a methylated dibenzoporphin

    International Nuclear Information System (INIS)

    Arabei, S.M.; Kuzmitsky, V.A.; Solovyov, K.N.

    2008-01-01

    The quasi-line low-temperature (4.2 K) fluorescence excitation spectra of 2,3,12,13-tetramethyldibenzo[g,q]porphin introduced into an n-octane matrix have been measured in the range of the S 2 0 electronic transition at selective fluorescence monitoring for the two main types of impurity centers (sites). A characteristic feature of these spectra is that a conglomerate of quasi-lines - a structured complex band - is observed instead of one 0-0 quasi-line of the S 2 0 transition. In this band, the intensity distributions for the two main sites considerably differ from each other. The occurrence of such conglomerates is interpreted as a result of nonadiabatic vibrational-electronic interaction between the vibronic S 2 and S 1 states (the complex vibronic analogue of the Fermi resonance). The frequencies and intensities of individual transitions determined from the deconvolution of complex conglomerates are used as the initial data for solving the inverse spectroscopic problem: the determination of the unperturbed electronic and vibrational levels of states involved in the resonance and the vibronic-interaction matrix elements between them. This problem is solved with a method developed previously. The experimental results and their analysis are compared to the analogous data obtained earlier for meso-tetraazaporphin and meso-tetrapropylporphin. The energy intervals between the S 2 and S 1 electronic levels (ΔE S 2 S 1 ) of the two main types of impurity centers formed by molecules of a given porphyrin in the crystal matrix are found to significantly differ from each other, the values of this difference (δΔE S 2 S 1 ) being considerably greater for tetramethyldibenzoporphin, δΔE S 2 S 1 =228cm -1 , than for the two other porphyrins. At the same time, the energies of the unperturbed vibrational states of the S 1 electronic level participating in the resonance are very close to each other for these two sites

  10. Vibrational analysis of various irotopes of L-alanyl-L-alanine in aqueous solution: Vibrational Absorption (VA), Vibrational Circular Dichroism (VCD), Raman and Raman Optical Activity (ROA) Spectra

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Nieminen, R.M.; Knapp-Mohammady, M.

    2003-01-01

    . DFT Becke3LYP/6-31G* theory has been used to determine the geometry, Hessian, atomic polar tensors (APT), and atomic axial tensors (AAT), and the electric dipole-electric dipole polarizability derivatives (EDEDPD), which are required for us to simulate the VA, VCD, and Raman spectra. The electric...

  11. Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes

    Energy Technology Data Exchange (ETDEWEB)

    Monahan, Daniele M.; Whaley-Mayda, Lukas; 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); Ishizaki, Akihito [Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki 444-8585 (Japan)

    2015-08-14

    Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear with increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.

  12. Quantifying the Performances of DFT for Predicting Vibrationally Resolved Optical Spectra: Asymmetric Fluoroborate Dyes as Working Examples.

    Science.gov (United States)

    Bednarska, Joanna; Zaleśny, Robert; Bartkowiak, Wojciech; Ośmiałowski, Borys; Medved', Miroslav; Jacquemin, Denis

    2017-09-12

    This article aims at a quantitative assessment of the performances of a panel of exchange-correlation functionals, including semilocal (BLYP and PBE), global hybrids (B3LYP, PBE0, M06, BHandHLYP, M06-2X, and M06-HF), and range-separated hybrids (CAM-B3LYP, LC-ωPBE, LC-BLYP, ωB97X, and ωB97X-D), in predicting the vibrationally resolved absorption spectra of BF 2 -carrying compounds. To this end, for 19 difluoroborates as examples, we use, as a metric, the vibrational reorganization energy (λ vib ) that can be determined based on the computationally efficient linear coupling model (a.k.a. vertical gradient method). The reference values of λ vib were determined by employing the CC2 method combined with the cc-pVTZ basis set for a representative subset of molecules. To validate the performances of CC2, comparisons with experimental data have been carried out as well. This study shows that the vibrational reorganization energy, involving Huang-Rhys factors and normal-mode frequencies, can indeed be used to quantify the reliability of functionals in the calculations of the vibrational fine structure of absorption bands, i.e., an accurate prediction of the vibrational reorganization energy leads to absorption band shapes better fitting the selected reference. The CAM-B3LYP, M06-2X, ωB97X-D, ωB97X, and BHandHLYP functionals all deliver vibrational reorganization energies with absolute relative errors smaller than 20% compared to CC2, whereas 10% accuracy can be achieved with the first three functionals. Indeed, the set of examined exchange-correlation functionals can be divided into three groups: (i) BLYP, B3LYP, PBE, PBE0, and M06 yield inaccurate band shapes (λ vib,TDDFT poor band topologies (λ vib,TDDFT > λ vib,CC2 ). This study also demonstrates that λ vib can be reliably estimated using the CC2 model and the relatively small cc-pVDZ basis set. Therefore, the linear coupling model combined with the CC2/cc-pVDZ level of theory can be used as a very efficient

  13. INTERPRETATION OF INFRARED VIBRATION-ROTATION SPECTRA OF INTERSTELLAR AND CIRCUMSTELLAR MOLECULES

    International Nuclear Information System (INIS)

    Lacy, John H.

    2013-01-01

    Infrared vibration-rotation lines can be valuable probes of interstellar and circumstellar molecules, especially symmetric molecules, which have no pure rotational transitions. But most such observations have been interpreted with an isothermal absorbing slab model, which leaves out important radiative transfer and molecular excitation effects. A more realistic non-LTE and non-isothermal radiative transfer model has been constructed. The results of this model are in much better agreement with the observations, including cases where lines in one branch of a vibration-rotation band are in absorption and another in emission. In general, conclusions based on the isothermal absorbing slab model can be very misleading, but the assumption of LTE may not lead to such large errors, particularly if the radiation field temperature is close to the gas temperature.

  14. Commutator perturbation method in the study of vibrational-rotational spectra of diatomic molecules

    International Nuclear Information System (INIS)

    Matamala-Vasquez, A.; Karwowski, J.

    2000-01-01

    The commutator perturbation method, an algebraic version of the Van Vleck-Primas perturbation method, expressed in terms of ladder operators, has been applied to solving the eigenvalue problem of the Hamiltonian describing the vibrational-rotational motion of a diatomic molecule. The physical model used in this work is based on Dunham's approach. The method facilitates obtaining both energies and eigenvectors in an algebraic way

  15. DNA oligonucleotide-cis-platin Binding: Ab initio interpretation of the vibrational spectra

    Czech Academy of Sciences Publication Activity Database

    Andrushchenko, Valery; Wieser, H.; Bouř, Petr

    2007-01-01

    Roč. 111, č. 39 (2007), s. 9714-9723 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400550702; GA ČR GA202/07/0732 Institutional research plan: CEZ:AV0Z40550506 Keywords : cis - platin * DNA * vibrational spektra * ab initio Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.918, year: 2007

  16. Theoretical Investigation on the Molecular Structure, Vibrational and NMR Spectra of N, N, 4-Tri chlorobenzenesulfonamide

    International Nuclear Information System (INIS)

    Cinar, M.

    2008-01-01

    In the present study, the structural properties of N,N,4-Tri chlorobenzenesulfonamide have been studied extensively using Density Functional Theory (DFT) employing B3LYP exchange correlation. The geometry of the molecule was fully optimized, vibrational spectrum was calculated and fundamental vibrations were assigned based on the scaled theoretical wavenumbers. The 1 H and 13 C nuclear magnetic resonance (NMR) chemical shifts of the compound were calculated using the Gauge-Invariant Atomic Orbital (GIAO) method. To investigate the basis set effects, calculations were performed at the 6-31G(d,p), 6-311G(d,p), 6-31++G(d,p) and 6-311++G(d,p) levels. Finally, geometric parameters, vibrational bands and isotropic chemical shifts were compared with available experimental data of compound. The fully optimized geometry of the molecule was found to be consistent with the X-ray crystal structure. The observed and calculated frequencies and chemical shifts were found to be in very good agreement. The computed results appear that the basis set has slight effect on the molecular geometry of N,N,4-Tri chlorobenzenesulfonamide

  17. A-VCI: A flexible method to efficiently compute vibrational spectra

    Science.gov (United States)

    Odunlami, Marc; Le Bris, Vincent; Bégué, Didier; Baraille, Isabelle; Coulaud, Olivier

    2017-06-01

    The adaptive vibrational configuration interaction algorithm has been introduced as a new method to efficiently reduce the dimension of the set of basis functions used in a vibrational configuration interaction process. It is based on the construction of nested bases for the discretization of the Hamiltonian operator according to a theoretical criterion that ensures the convergence of the method. In the present work, the Hamiltonian is written as a sum of products of operators. The purpose of this paper is to study the properties and outline the performance details of the main steps of the algorithm. New parameters have been incorporated to increase flexibility, and their influence has been thoroughly investigated. The robustness and reliability of the method are demonstrated for the computation of the vibrational spectrum up to 3000 cm-1 of a widely studied 6-atom molecule (acetonitrile). Our results are compared to the most accurate up to date computation; we also give a new reference calculation for future work on this system. The algorithm has also been applied to a more challenging 7-atom molecule (ethylene oxide). The computed spectrum up to 3200 cm-1 is the most accurate computation that exists today on such systems.

  18. Molecular structure, vibrational spectra and DFT computational studies of melaminium N-acetylglycinate dihydrate

    Science.gov (United States)

    Tanak, H.; Pawlus, K.; Marchewka, M. K.

    2016-10-01

    Melaminium N-acetylglycinate dihydrate, an organic material has been synthesized and characterized by X-ray diffraction, FT-IR, and FT-Raman spectroscopies for the protiated and deuteriated crystals. The title complex crystallizes in the triclinic system, and the space group is P-1 with a = 5.642(1) Å, b = 7.773(2) Å, c = 15.775(3) Å, α = 77.28(1)°, β = 84.00(1)°, γ = 73.43(1)° and Z = 2. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional method (B3LYP) with the 6-311++G(d,p) basis set. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. The intermolecular hydrogen bonding interactions of the title compound have been investigated using the natural bonding orbital analysis. It reveals that the O-H···O, N-H···N and N-H···O intermolecular interactions significantly influence crystal packing of this molecule. The non-linear optical properties are also addressed theoretically. The predicted NLO properties of the title compound are much greater than ones of urea. In addition, DFT calculations of the title compound, molecular electrostatic potential, thermodynamic properties, frontier orbitals and chemical reactivity descriptors were also performed at 6-311++G(d,p) level of theory.

  19. 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.

  20. Vibrational spectra of the hydrated carbonate minerals ikaite, monohydrocalcite, lansfordite and nesquehonite

    Science.gov (United States)

    Coleyshaw, Esther E.; Crump, Gregory; Griffith, William P.

    2003-08-01

    The Raman (200-4000 cm -1) and infrared (600-4000 cm -1) spectra of four rare carbonate hydrate minerals are reported. These are naturally occurring and synthetic ikaite CaCO 3 · 6H 2O, and nesquehonite MgCO 3 · 3H 2O; natural monohydrocalcite CaCO 3 · H 2O, and synthetic lansfordite MgCO 3 · 5H 2O. The spectra of synthetic ikaite partially substituted with 2H 2O and also with 13C were measured, as were those of synthetic deuteriated nesquehonite. Spectra of ikaite and lansfordite, both of which decompose at room temperatures, were measured below 0 °C. Assignments of fundamental modes are proposed.

  1. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene III. 3,3-Dimethyl-1-(trimethylsilyl)cyclopropene

    Science.gov (United States)

    De Maré, G. R.; Panchenko, Yu. N.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-07-01

    The experimental Raman and IR vibrational spectra of 3,3-dimethyl-1-(trimethylsilyl)cyclopropene in the liquid phase were recorded. Total geometry optimisation was carried out at the HF/6-31G* level and the HF/6-31G*//HF/6-31G* force field was computed. This force field was corrected by scale factors determined previously (using Pulay's method) for correction of the HF/6-31G*//HF/6-31G* force fields of 3,3-dimethylbutene-1, 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene. The theoretical vibrational frequencies calculated from the scaled quantum mechanical force field and the theoretical intensities obtained from the quantum mechanical calculation were used to construct predicted spectra and to perform the vibrational analysis of the experimental spectra.

  2. Studies on molecular structure, vibrational spectra and molecular docking analysis of 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate

    Science.gov (United States)

    Suresh, D. M.; Amalanathan, M.; Hubert Joe, I.; Bena Jothy, V.; Diao, Yun-Peng

    2014-09-01

    The molecular structure, vibrational analysis and molecular docking analysis of the 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate (MDDNAB) molecule have been carried out using FT-IR and FT-Raman spectroscopic techniques and DFT method. The equilibrium geometry, harmonic vibrational wave numbers, various bonding features have been computed using density functional method. The calculated molecular geometry has been compared with experimental data. The detailed interpretation of the vibrational spectra has been carried out by using VEDA program. The hyper-conjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The simulated FT-IR and FT-Raman spectra satisfactorily coincide with the experimental spectra. The PES and charge analysis have been made. The molecular docking was done to identify the binding energy and the Hydrogen bonding with the cancer protein molecule.

  3. Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

    Energy Technology Data Exchange (ETDEWEB)

    Fujihashi, Yuta; Ishizaki, Akihito, E-mail: ishizaki@ims.ac.jp [Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki 444-8585 (Japan); Fleming, Graham R. [Department of Chemistry, University of California, Berkeley and Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-06-07

    Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

  4. Vibrational absorption spectra, DFT and SCC-DFTB conformational study and analysis of [Leu]enkephalin

    DEFF Research Database (Denmark)

    Abdali, Salim; Niehaus, T.A.; Jalkanen, Karl J.

    2003-01-01

    . Ab initio (DFT at the B3LYP/6-31G* level of theory) and semi-empirical (SCC-DFTB) with and without dispersion correction were applied to simulate the VA spectra of [Leu] enkephalin. In these calculations structures taken from X-ray measurements for different conformers of the molecule were used...

  5. On the effects of transforming the vibrational spectra of molecular systems under microwave radiation

    International Nuclear Information System (INIS)

    Serikov, A.A.

    1993-01-01

    This problem is analyzed within the quantum-classical theory of molecular spectra. It is shown that the above-mentioned spectrum transformation could be, in principle, realized in macromolecular systems with strong interaction, and attention is drawn to the resonance character of the effect. (author). 19 refs., 1 fig

  6. Molecular conformational analysis, vibrational spectra and normal coordinate analysis of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene based on density functional theory calculations.

    Science.gov (United States)

    Joseph, Lynnette; Sajan, D; Chaitanya, K; Isac, Jayakumary

    2014-03-25

    The conformational behavior and structural stability of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene (TDBE) were investigated by using density functional theory (DFT) method with the B3LYP/6-311++G(d,p) basis set combination. The vibrational wavenumbers of TDBE were computed at DFT level and complete vibrational assignments were made on the basis of normal coordinate analysis calculations (NCA). The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compound. The infrared and Raman spectra were also predicted from the calculated intensities. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Rotational and vibrational synthetic spectra of linear parent molecules in comets

    International Nuclear Information System (INIS)

    Crovisier, J.

    1987-01-01

    We evaluate and model the excitation conditions of linear parent molecules in cometary atmospheres. The model is valid for most linear molecules without electronic angular momentum. It takes into account collisions and infrared excitation. The molecule rotational population distribution is computed as a function of distance to nucleus. The line intensities of the strongest parallel and perpendicular fundamental vibrational bands, as well as the pure rotational lines, can then be evaluated. This model is applied to several candidate parent molecules, for observing conditions corresponding to available or planned instruments, either ground-based or aboard aircrafts, satellites or space probes

  8. Vibrational spectra and thermal rectification in three-dimensional anharmonic lattices

    International Nuclear Information System (INIS)

    Lan Jinghua; Li Baowen

    2007-01-01

    We study thermal rectification in a three-dimensional model consisting of two segments of anharmonic lattices. One segment consists of layers of harmonic oscillator arrays coupled to a substrate potential, which is a three-dimensional Frenkel-Kontorova model, and the other segment is a three-dimensional Fermi-Pasta-Ulam model. We study the vibrational bands of the two lattices analytically and numerically, and find that, by choosing the system parameters properly, the rectification can be as high as a few thousands, which is high enough to be observed in experiment. Possible experiments in nanostructures are discussed

  9. Vibrational Spectra and Density functional calculation of Organic Nonlinear Optic Crystal p-Amino Acetanilide

    Energy Technology Data Exchange (ETDEWEB)

    Saja, D; Joe, I Hubert; Jayakumar, V S [Department of Physics, Mar Ivanios College, Thiruvananthapuram-695015, Kerala (India)

    2006-01-01

    The NIR-FT Raman, FT-IR spectral analysis of potential NLO material P-Amino Acetanilide is carried out by density functional computations. The optimized geometry shows that NH2 and NHCOCH3 groups substituted in para position of phenyl ring are non-planar which predicts maximum conjugation of molecule with donor and acceptor groups. Vibrational analysis reveals that simultaneous IR and Raman activation of the phenyl ring modes also provide evidence for the charge transfer interaction between the donors and the acceptor can make the molecule highly polarized and the intra molecular charge transfer interaction must be responsible for the NLO properties of PAA.

  10. Vibrational Spectra and Density functional calculation of Organic Nonlinear Optic Crystal p-Amino Acetanilide

    International Nuclear Information System (INIS)

    Saja, D; Joe, I Hubert; Jayakumar, V S

    2006-01-01

    The NIR-FT Raman, FT-IR spectral analysis of potential NLO material P-Amino Acetanilide is carried out by density functional computations. The optimized geometry shows that NH2 and NHCOCH3 groups substituted in para position of phenyl ring are non-planar which predicts maximum conjugation of molecule with donor and acceptor groups. Vibrational analysis reveals that simultaneous IR and Raman activation of the phenyl ring modes also provide evidence for the charge transfer interaction between the donors and the acceptor can make the molecule highly polarized and the intra molecular charge transfer interaction must be responsible for the NLO properties of PAA

  11. Vibrational spectra of 1-hydroxy- and 1,4-dihydroxyanthraquinones and their magnesium chelate complexes. I. Isotopic effects of OH/OD and 24Mg/26Mg substitutions

    International Nuclear Information System (INIS)

    Kirszenbaum, Marek

    1977-01-01

    The vibrational spectra of 1-hydroxy- and 1,4-dihydroxyanthraquinones, their deuterated derivatives and their 24 Mg/ 26 Mg chelate complexes are examined in the spectral region 1700-250cm -1 . The study of deuteroxyanthraquinones allow an assignment of the OH/OD group vibrations and show the multiple coupling of the delta OH vibrations with the vCC and delta CH quinonic vibrations. These results lead to a modification of some spectral assignments of magnesium chelate complexe of 1-OH-AQ. The isotopic 24 Mg/ 26 Mg substitution enables the chelate ring vibrations which depend on the motions of the magnesium atom to be observed. The vC=O and vC-O vibrations frequencies of magnesium chelate complexe [Mg(1,4-O 2 -AQ)]sub(n) show an important difference of the chelate ring electronic state in comparison of those of 1,4-(OH) 2 -AQ. The discussion of the infrared and Raman spectra in the Mg-O vibrations region lead to the conclusion that the configuration of oxygens arround the magnesium is tetrahedral [fr

  12. Microwave, infrared and Raman spectra, adjusted r{sub 0} structural parameters, conformational stability, and vibrational assignment of cyclopropylfluorosilane

    Energy Technology Data Exchange (ETDEWEB)

    Panikar, Savitha S. [Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 (United States); Guirgis, Gamil A.; Eddens, Matthew T.; Dukes, Horace W. [Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424 (United States); Conrad, Andrew R.; Tubergen, Michael J. [Department of Chemistry, Kent State University, Kent, OH 44242 (United States); Gounev, Todor K. [Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 (United States); Durig, James R., E-mail: durigj@umkc.edu [Department of Chemistry, University of Missouri-Kansas City, Kansas City, MO 64110 (United States)

    2013-03-29

    Highlights: ► The most stable gauche conformer has been identified from microwave spectra. ► Enthalpy difference has been determined between the two forms. ► Adjusted r{sub 0} structures were obtained for the gauche form. ► Ab initio calculations were performed for the two conformers. - Abstract: FT-microwave, infrared spectra of gas and Raman spectra of liquid for cyclopropylfluorosilane, c-C{sub 3}H{sub 5}SiH{sub 2}F have been recorded. 51 transitions for the {sup 28}Si, {sup 29}Si, and {sup 30}Si isotopomers have been assigned for the gauche conformer. Enthalpy differences in xenon solution by variable temperature infrared spectra between the more stable gauche and lesser stable cis form gave 109 ± 9 cm{sup −1}. From the microwave rotational constants for the three isotopomers ({sup 28}Si, {sup 29}Si, {sup 30}Si) combined with structural parameters predicted from MP2(full)/6-311+G(d, p) calculations, adjusted r{sub 0} structural parameters were obtained for the gauche conformer. The heavy atom distances (Å): Si–C{sub 2} = 1.836(3); C{sub 2}–C{sub 4} = 1.525(3); C{sub 2}–C{sub 5} = 1.519(3); C{sub 4}–C{sub 5} = 1.494(3); Si–F = 1.594(3) and angles (°): ∠CSiF = 111.2(5); ∠SiC{sub 2}C{sub 4} = 117.5(5); ∠SiC{sub 2}C{sub 5} = 119.2(5). To support the vibrational assignments, MP2(full)/6-31G(d) calculations were carried out. Results are discussed and compared to the corresponding properties of some similar molecules.

  13. High-pressure Raman study of vibrational spectra in crystalline acetanilide

    Science.gov (United States)

    Sakai, Masamichi; Kuroda, Noritaka; Nishina, Yuichiro

    1993-01-01

    We have studied the effect of pressure on the low-frequency lattice modes and the amide-I (N-CO stretching) vibrational modes in crystalline acetanilide (C6H5NHCOCH3) in the temperature range 80-300 K by means of Raman spectroscopy. The Raman intensity of the 1650-cm-1 band, which appears upon cooling, is enhanced by applying pressure. The energy difference between the amide-I phonon (Ag mode) and the 1650-cm-1 bands does not change appreciably under pressure up to at least 4 GPa. These results are analyzed in terms of the self-trapped model in which a single lattice mode couples with the amide-I excitation by taking into account the effect of pressure on the low-frequency lattice modes and on the dipole-dipole interactions associated with the amide-I vibration. A band is observed at 30 cm-1 below the amide-I phonon band at low temperatures with a pressure above ~2 GPa.

  14. Synthesis, crystal structure, vibrational spectra and theoretical calculations of quantum chemistry of a potential antimicrobial Meldrum's acid derivative

    Science.gov (United States)

    Campelo, M. J. M.; Freire, P. T. C.; Mendes Filho, J.; de Toledo, T. A.; Teixeira, A. M. R.; da Silva, L. E.; Bento, R. R. F.; Faria, J. L. B.; Pizani, P. S.; Gusmão, G. O. M.; Coutinho, H. D. M.; Oliveira, M. T. A.

    2017-10-01

    A new derivative of Meldrum's acid 5-((5-chloropyridin-2-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (CYMM) of molecular formula C12H11ClN2O4 was synthesized and structurally characterized using single crystal X-ray diffraction technique. The vibrational properties of the crystal were studied by Fourier Transform infrared (FT-IR), Fourier Transform Raman (FT-Raman) techniques and theoretical calculations of quantum chemistry using Density functional theory (DFT) and Density functional perturbation theory (DFPT). A comparison with experimental spectra allowed the assignment of all the normal modes. The descriptions of the normal modes were carried by means of potential energy distribution (PED). Additionally, analysis of the antimicrobial activity and antibiotic resistance modulatory activity was carried out to evaluate the antibacterial potential of the CYMM.

  15. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Science.gov (United States)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-07-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  16. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    International Nuclear Information System (INIS)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-01-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N 2 , Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  17. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Energy Technology Data Exchange (ETDEWEB)

    Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui [CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

    2016-07-07

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2}, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  18. Optimized geometry, vibration (IR and Raman spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

    Directory of Open Access Journals (Sweden)

    Tamer Ömer

    2016-03-01

    Full Text Available The molecular modeling of p-nitroanilinium perchlorate molecule was carried out by using B3LYP and HSEH1PBE levels of density functional theory (DFT. The IR and Raman spectra were simulated and the assignments of vibrational modes were performed on the basis of relative contribution of various internal co-ordinates. NBO analysis was performed to demonstrate charge transfer, conjugative interactions and the formation of intramolecular hydrogen bonding interactions within PNAPC. Obtained large dipole moment values showed that PNAPC is a highly polarizable complex, and the charge transfer occurs within PNAPC. Hydrogen bonding and charge transfer interactions were also displayed by small HOMO-LUMO gap and molecular electrostatic potential (MEP surface. The strong evidences that the material can be used as an efficient nonlinear optical (NLO material of PNAPC were demonstrated by considerable polarizability and hyperpolarizability values obtained at DFT levels.

  19. The structure, vibrational spectra and nonlinear optical properties of the L-lysine × tartaric acid complex—Theoretical studies

    Science.gov (United States)

    Drozd, M.; Marchewka, M. K.

    2006-05-01

    The room temperature X-ray studies of L-lysine × tartaric acid complex are not unambiguous. The disorder of three atoms of carbon in L-lysine molecule is observed. These X-ray studies are ambiguous. The theoretical geometry study performed by DFT methods explain the most doubts which are connected with crystallographic measurements. The theoretical vibrational frequencies and potential energy distribution (PED) of L-lysine × tartaric acid were calculated by B3LYP method. The calculated frequencies were compared with experimental measured IR spectra. The complete assignment of the bands has been made on the basis of the calculated PED. The restricted Hartee-Fock (RHF) methods were used for calculation of the hyperpolarizability for investigated compound. The theoretical results are compared with experimental value of β.

  20. The effect of nonlocal dielectric response on the surface-enhanced Raman and fluorescence spectra of molecular systems

    Science.gov (United States)

    Wei, Yong; Pei, Huan; Li, Li; Zhu, Yanying

    2018-06-01

    We present a theoretical study on the influence of the nonlocal dielectric response on surface-enhanced resonant Raman scattering (SERRS) and fluorescence (SEF) spectra of a model molecule confined in the center of a Ag nanoparticle (NP) dimer. In the simulations, the nonlocal dielectric response caused by the electron–hole pair generation in Ag NPs was computed with the d-parameter theory, and the scattering spectra of a model molecule representing the commonly used fluorescent dye rhodamine 6G (R6G) were obtained by density-matrix calculations. The influence of the separation between Ag NP dimers on the damping rate and scattering spectra with and without the nonlocal response were systematically analyzed. The results show that the nonlocal dielectric response is very sensitive to the gap distance of the NP dimers, and it undergoes much faster decay with the increase of the separation than the radiative and energy transfer rates. The Raman and fluorescence peaks as simulated with the nonlocal dielectric response are relative weaker than that without the nonlocal effect for smaller NP separations because the extra decay rates of the nonlocal effect could reduce both the population of the excited state and the interband coherence between the ground and excited states. Our result also indicates that the nonlocal effect is more prominent on the SEF process than the SERRS process.

  1. Classification of different kinds of pesticide residues on lettuce based on fluorescence spectra and WT-BCC-SVM algorithm

    Science.gov (United States)

    Zhou, Xin; Jun, Sun; Zhang, Bing; Jun, Wu

    2017-07-01

    In order to improve the reliability of the spectrum feature extracted by wavelet transform, a method combining wavelet transform (WT) with bacterial colony chemotaxis algorithm and support vector machine (BCC-SVM) algorithm (WT-BCC-SVM) was proposed in this paper. Besides, we aimed to identify different kinds of pesticide residues on lettuce leaves in a novel and rapid non-destructive way by using fluorescence spectra technology. The fluorescence spectral data of 150 lettuce leaf samples of five different kinds of pesticide residues on the surface of lettuce were obtained using Cary Eclipse fluorescence spectrometer. Standard normalized variable detrending (SNV detrending), Savitzky-Golay coupled with Standard normalized variable detrending (SG-SNV detrending) were used to preprocess the raw spectra, respectively. Bacterial colony chemotaxis combined with support vector machine (BCC-SVM) and support vector machine (SVM) classification models were established based on full spectra (FS) and wavelet transform characteristics (WTC), respectively. Moreover, WTC were selected by WT. The results showed that the accuracy of training set, calibration set and the prediction set of the best optimal classification model (SG-SNV detrending-WT-BCC-SVM) were 100%, 98% and 93.33%, respectively. In addition, the results indicated that it was feasible to use WT-BCC-SVM to establish diagnostic model of different kinds of pesticide residues on lettuce leaves.

  2. Study on structure, vibrational analysis and molecular characteristics of some halogen substituted azido-phenylethanones using FTIR spectra and DFT

    Science.gov (United States)

    Prashanth, J.; Reddy, Byru Venkatram

    2018-03-01

    The Fourier transform infrared (FTIR) spectra of organic compounds 4-fluoro-2-azido-1-phenylethanone (FAP), 4-chloro-2-azido-1-phenylethanone (CAP) and 4-bromo-2-azido-1-phenylethanone (BAP) have been recorded in the region 4000-400 cm-1. The optimized molecular structure for global minimum energy of the titled molecules is determined by evaluating torsional potentials as a function of rotation angle about free rotation bonds among the substituent groups subjecting them to DFT employing B3LYP functional with 6-311++G (d,p) basis set. The vibrational frequencies along with infrared intensities are computed by SQM procedure. The rms error between observed and calculated frequencies is found to be 9.27, 8.17 and 7.95 cm-1 for FAP, CAP and BAP, respectively which shows good agreement between experimental and scaled values of calculated frequencies obtained by DFT. The vibrational assignments of all the fundamental bands of each molecule are made unambiguously using PED and eigen vectors obtained in the computations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the titled molecules exhibit NLO behaviour and hence may be considered for potential applicants for the development of NLO materials. HOMO and LUMO energies evaluated in the study demonstrate chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyper conjugative interactions and charge delocalization. The molecular electrostatic surface potential (MESP) and thermodynamic parameters are also evaluated.

  3. Comparison of different eigensolvers for calculating vibrational spectra using low-rank, sum-of-product basis functions

    Science.gov (United States)

    Leclerc, Arnaud; Thomas, Phillip S.; Carrington, Tucker

    2017-08-01

    Vibrational spectra and wavefunctions of polyatomic molecules can be calculated at low memory cost using low-rank sum-of-product (SOP) decompositions to represent basis functions generated using an iterative eigensolver. Using a SOP tensor format does not determine the iterative eigensolver. The choice of the interative eigensolver is limited by the need to restrict the rank of the SOP basis functions at every stage of the calculation. We have adapted, implemented and compared different reduced-rank algorithms based on standard iterative methods (block-Davidson algorithm, Chebyshev iteration) to calculate vibrational energy levels and wavefunctions of the 12-dimensional acetonitrile molecule. The effect of using low-rank SOP basis functions on the different methods is analysed and the numerical results are compared with those obtained with the reduced rank block power method. Relative merits of the different algorithms are presented, showing that the advantage of using a more sophisticated method, although mitigated by the use of reduced-rank SOP functions, is noticeable in terms of CPU time.

  4. Using violet laser-induced chlorophyll fluorescence emission spectra for crop yield assessment of cowpea (Vigna unguiculata (L) Walp) varieties

    Science.gov (United States)

    Anderson, Benjamin; Buah-Bassuah, Paul K.; Tetteh, Jonathan P.

    2004-07-01

    The use of violet laser-induced chlorophyll fluorescence (LICF) emission spectra to monitor the growth of five varieties of cowpea in the University of Cape Coast Botanical Garden is presented. Radiation from a continuous-wave violet laser diode emitting at 396 nm through a fibre is closely incident on in vivo leaves of cowpea to excite chlorophyll fluorescence, which is detected by an integrated spectrometer with CCD readout. The chlorophyll fluorescence spectra with peaks at 683 and 731 nm were used for growth monitoring of the cowpea plants over three weeks and analysed using Gaussian spectral functions with curve fitted parameters to determine the peak positions, area under the spectral curve and the intensity ratio F683/F731. The variation in the intensity ratio of the chlorophyll bands showed sensitive changes indicating the photosynthetic activity of the cowpea varieties. A discussion of the fluorescence result as compared to conventional assessment is presented with regard to discrimination between the cowpea varieties in terms of crop yield performance.

  5. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra

    Science.gov (United States)

    Goun, Alexei; Bondar, Denys I.; Er, Ali O.; Quine, Zachary; Rabitz, Herschel A.

    2016-05-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters.

  6. Temperature dependence of the vibrational spectra of acetanilide: Davydov solitons or Fermi coupling

    Energy Technology Data Exchange (ETDEWEB)

    Johnston, C.T.; Swanson, B.I.

    1985-03-15

    The unusual temperature dependence of the amide-I region in the IR spectrum of acetanilide (C/sub 6/H/sub 5/NHCOCH/sub 3/) has recently been attributed to a self-trapped Davydov-like soliton. The temperature dependence of the single-crystal Raman scattering from acetanilide and its N-D and /sup 13/C-O substituted analogs in the phonon and internal mode regions has now been studied. The behavior of the amide-I region in the Raman spectra of the normal isotopic species is similar to that observed earlier in infrared studies. However, on the basis of results obtained from the N-D and /sup 13/C-O substituted species the unusual temperature dependence in the 1650 cm/sup -1/ region has been attributed to Fermi coupling of the amide-I fundamental and a combination band involving the in-plane N-H deformation and a low-frequency torsional mode. As temperature is lowered, the strong blue-shift of the torsional mode results in a commensurate blue-shift in the combination level thereby increasing the Fermi coupling. Temperature tuning of the Fermi coupling results in the anomalous intensity changes observed in the IR and Raman spectra of the amide-I region for the normal isotopic species. 20 references, 3 figures.

  7. Temperature dependence of the vibrational spectra of acetanilide: Davydov solitons or Fermi coupling?

    Science.gov (United States)

    Johnston, Clifford T.; Swanson, Basil I.

    1985-03-01

    The unusual temperature dependence of the amide-I region in the IR spectrum of acetanilide (C 6H 5NHCOCH 3) has recently been attributed to a self-trapped Davydov-like soliton. The temperature dependence of the single-crystal Raman scattering, from acetanilide and its ND and 13CO substituted analogs in the phonon and internal mode regions has now been studied. The behavior of the amide-I region in the Raman spectra of the normal isotopic species is similar to that observed earlier in infrared studies. However, on the basis of results obtained from the ND and 13CO substituted species the unusual temperature dependence in the 1650 cm -1 region has been attributed to Fermi coupling of the amide-I fundamental and a combination band involving the in-plane NH deformation and a low-frequency torsional mode. As temperature is lowered, the strong blue-shift of the torsional mode results in a commensurate blue-shift in the combination level thereby increasing the Fermi coupling. Temperature tuning of the Fermi coupling results in the anomalous intensity changes observed in the IR and Raman spectra of the amide-I region for the normal isotopic species.

  8. Resonance fluorescence spectra of a three-level atom driven by two strong laser fields

    International Nuclear Information System (INIS)

    Peng Jinsheng.

    1986-12-01

    The resonance fluorescence of a three-level atom interacted with two high-power laser fields is investigated in strong field approximation. The fluorescence distribution is obtained by means of the theory of dressing transformation. (author). 15 refs, 2 figs

  9. Linear response properties required to simulate vibrational spectra of biomolecules in various media: (R)-phenyloxirane (A comparative theoretical and spectroscopic vibrational study)

    DEFF Research Database (Denmark)

    Jalkanen, Karl J.; Jürgensen, Vibeke Würtz; Degtyarenko, I.M.

    2005-01-01

    We here present a combined VA, VCD, Raman and ROA vibrational study of phenyloxirane. We have simulated the vibrational absorption (VA), also called IR, vibrational circular dichroism (VCD), Raman scattering and Raman optical activity (ROA) intensities utilizing the density functional theory (DFT...

  10. Theoretical Investigation of the Effect of the Rare Gas Matrices on the Vibrational Spectra of Solvated Molecular Ions: Cu+CO

    Czech Academy of Sciences Publication Activity Database

    Bludský, Ota; Šilhan, Martin; Nachtigall, Petr

    2002-01-01

    Roč. 117, č. 20 (2002), s. 9298-9305 ISSN 0021-9606 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : vibrational spectra * solvated molecular ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.998, year: 2002

  11. Rotational and vibrational spectra of ethynol from quantum-mechanical calculations

    Science.gov (United States)

    Defrees, D. J.; Mclean, A. D.

    1982-01-01

    It is noted that ethynol (HCCOH), despite the theoretical prediction of its stability to tautomerization to ketene, has thus far not been observed. It is shown here that the identification of this unknown molecule, both in space and in the laboratory, can be aided by an ab initio calculation of spectroscopic parameters. At the HF/3-21G level, harmonic vibrational frequencies are computed by way of analytic second differentiation of the Hartee-Fock (HF) energy with respect to the nuclear coordinates. After applying an empirical scale factor, the resultant frequencies are (per cm) 473, 517, 773, 841, 1003, 1217, 2206, 3285, and 3418. The computed dipole moment at the CISD/DZ+P level is 1.79 D. At the CISD+Q/DZ+P level, the molecule's rotational constants are determined. After scaling by empirical correction factors, they are used in deriving the 4(04) - 3(03) frequency of 76.81 + or - 0.3 GHz with a triplet splitting of 0.30 + or - 0.01 GHz. The triplet splitting involves 4(14) - 3(13) and 4(13) - 3(12) relative to the 4(04) - 3(03) transition as the central line.

  12. Vibrational spectra of mixed oxides of Ln2MgTiO6 composition

    International Nuclear Information System (INIS)

    Porotnikov, N.V.; German, M.; Kovba, L.M.

    1984-01-01

    In the range 33-4000 cm -1 IR and Raman spectra of complex oxides of the composition Ln 2 MgTiO 6 (Ln=La-Yb and Y) have been studied. Using the Magnesium isotope-substituted compositions Lasub(2)sup(24,26)MgTiOsub(6), Smsub(2)sup(24,26)MgTiOsub(6) and Ybsub(2)sup(24,26)MgTiOsub(6), it has been shoWn that in Ln 2 MgTiO 6 titanium and magnesium ions are located in sites With octahedral coordination, of rare earth ions highly-coordinated polyhedrons with coordination number 10-12 are characteristic

  13. ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethite.

    Science.gov (United States)

    Kubicki, James D; Paul, Kristian W; Kabalan, Lara; Zhu, Qing; Mrozik, Michael K; Aryanpour, Masoud; Pierre-Louis, Andro-Marc; Strongin, Daniel R

    2012-10-16

    Periodic plane-wave density functional theory (DFT) and molecular cluster hybrid molecular orbital-DFT (MO-DFT) calculations were performed on models of phosphate surface complexes on the (100), (010), (001), (101), and (210) surfaces of α-FeOOH (goethite). Binding energies of monodentate and bidentate HPO(4)(2-) surface complexes were compared to H(2)PO(4)(-) outer-sphere complexes. Both the average potential energies from DFT molecular dynamics (DFT-MD) simulations and energy minimizations were used to estimate adsorption energies for each configuration. Molecular clusters were extracted from the energy-minimized structures of the periodic systems and subjected to energy reminimization and frequency analysis with MO-DFT. The modeled P-O and P---Fe distances were consistent with EXAFS data for the arsenate oxyanion that is an analog of phosphate, and the interatomic distances predicted by the clusters were similar to those of the periodic models. Calculated vibrational frequencies from these clusters were then correlated with observed infrared bands. Configurations that resulted in favorable adsorption energies were also found to produce theoretical vibrational frequencies that correlated well with experiment. The relative stability of monodentate versus bidentate configurations was a function of the goethite surface under consideration. Overall, our results show that phosphate adsorption onto goethite occurs as a variety of surface complexes depending on the habit of the mineral (i.e., surfaces present) and solution pH. Previous IR spectroscopic studies may have been difficult to interpret because the observed spectra averaged the structural properties of three or more configurations on any given sample with multiple surfaces.

  14. Molecular structure, vibrational spectra and photochemistry of 5-mercapto-1-methyltetrazole

    Science.gov (United States)

    Gómez-Zavaglia, A.; Reva, I. D.; Frija, L.; Cristiano, M. L.; Fausto, R.

    2006-04-01

    In this work, 5-mercapto-1-methyltetrazole was studied by low temperature matrix-isolation and solid-state infrared spectroscopy, DFT(B3LYP)/6-311++G(d,p) calculations and photochemical methods. In the low temperature neat solid phase and isolated in an argon matrix, the compound was found to exist in the 1-methyl-1,4-dihydro-5 H-tetrazole-5-thione tautomeric form. The infrared spectra of the compound were fully assigned and correlated with structural properties. In situ UV-irradiation ( λ>235 nm) of the matrix-isolated monomer is shown to induce different photochemical processes, all of them involving cleavage of the tetrazole ring: e.g. (1) molecular nitrogen expulsion, with production of 1-methyl-1 H-diazirene-3-thiol, which is produced in two different conformers; (2) ring cleavage leading to production of methyl isothiocyanate and azide; (3) simultaneous elimination of nitrogen and sulphur with production of N-methylcarbodiimide. Following these photoprocesses, subsequent reactions occur, leading to production of methyl diazene, carbon monosulphide and nitrogen hydride. Spectroscopic evidence of the production of the above-mentioned chemical species is provided.

  15. The multi-resolution capability of Tchebichef moments and its applications to the analysis of fluorescence excitation-emission spectra

    Science.gov (United States)

    Li, Bao Qiong; Wang, Xue; Li Xu, Min; Zhai, Hong Lin; Chen, Jing; Liu, Jin Jin

    2018-01-01

    Fluorescence spectroscopy with an excitation-emission matrix (EEM) is a fast and inexpensive technique and has been applied to the detection of a very wide range of analytes. However, serious scattering and overlapping signals hinder the applications of EEM spectra. In this contribution, the multi-resolution capability of Tchebichef moments was investigated in depth and applied to the analysis of two EEM data sets (data set 1 consisted of valine-tyrosine-valine, tryptophan-glycine and phenylalanine, and data set 2 included vitamin B1, vitamin B2 and vitamin B6) for the first time. By means of the Tchebichef moments with different orders, the different information in the EEM spectra can be represented. It is owing to this multi-resolution capability that the overlapping problem was solved, and the information of chemicals and scatterings were separated. The obtained results demonstrated that the Tchebichef moment method is very effective, which provides a promising tool for the analysis of EEM spectra. It is expected that the applications of Tchebichef moment method could be developed and extended in complex systems such as biological fluids, food, environment and others to deal with the practical problems (overlapped peaks, unknown interferences, baseline drifts, and so on) with other spectra.

  16. Quantum chemical density functional theory studies on the molecular structure and vibrational spectra of Gallic acid imprinted polymers

    Science.gov (United States)

    Pardeshi, Sushma; Dhodapkar, Rita; Kumar, Anupama

    2013-12-01

    Gallic acid (GA) is known by its antioxidant, anticarcinogenic properties and scavenger activity against several types of harmful free radicals. Molecularly imprinted polymers (MIPs) are used in separation of a pure compound from complex matrices. A stable template-monomer complex generates the MIPs with the highest affinity and selectivity for the template. The quantum chemical computations based on density functional theory (DFT) was used on the template Gallic acid (GA), monomer acrylic acid (AA) and GA-AA complex to study the nature of interactions involved in the GA-AA complex. B3LYP/6-31+G(2d,2p) model chemistry was used to optimize their structures and frequency calculations. The effect of porogen acetonitrile (ACN) on complex formation was included by using polarizable continuum model (PCM). The results demonstrated the formation of a stable GA-AA complex through the intermolecular hydrogen bonding between carboxylic acid groups of GA and AA. The Mulliken atomic charge analysis and simulated vibrational spectra also supported the stable hydrogen bonding interaction between the carboxylic acid groups of GA and AA with minimal interference of porogen ACN. Further, simulations on GA-AA mole ratio revealed that 1:4 GA-AA was optimum for synthesis of MIP for GA.

  17. Molecular structure, vibrational spectra and quantum chemical MP2/DFT studies toward the rational design of hydroxyurea imprinted polymer

    Science.gov (United States)

    Prasad, Bhim Bali; Rai, Garima

    2013-03-01

    In this study, both experimental and theoretical vibrational spectra of template (hydroxyurea, HU), monomer (N-(4,6-bisacryloyl amino-[1,3,5] triazine-2-yl-)-acryl amide, TAT), and HU-TAT complexes were compared and these were respectively found to be in good agreement. Binding energies of HU, when complexed with different monomers, were computed using second order Moller Plesset theory (MP2) at 6-311++G(d,p) level both in the gas as well as solution phases. HU is an antineoplastic agent extensively being used in the treatment of polycythaemia Vera and thrombocythemia. It is also used to reduce the frequency of painful attacks in sickle cell anemia. It has antiretroviral property in disease like AIDS. All spectral characterizations were made using Density Functional Theory (DFT) at B3LYP employing 6-31+g(2d, 2p) basis set. The theoretical values for 13C and 1H NMR chemical shifts were found to be in accordance with the corresponding experimental values. Of all different monomers studied for the synthesis of molecularly imprinted polymer (MIP) systems, the monomer TAT (2 mol) was typically found to have a best binding score requisite for complexation with HU (1 mol) at the ground state.

  18. X-ray, MP2 and DFT studies of the structure and vibrational spectra of trigonellinium chloride

    International Nuclear Information System (INIS)

    Szafran, M.; Koput, J.; Dega-Szafran, Z.; Katrusiak, A.; Pankowski, M.; Stobiecka, K.

    2003-01-01

    The effects of hydrogen bonding, inter- and intramolecular electrostatic interactions on the conformation of trigonellinium chloride, TRGH...Cl, in the crystal and on that of a single molecule have been studied by X-ray diffraction, FT-IR, Raman, 1 H and 13 C NMR spectroscopies, and by MP2 and DFT calculations. In the crystal, the Cl - anion is connected with protonated trigonelline via hydrogen bond, O-H...Cl - =2.915(3) Angst, and three N + ...Cl - intermolecular electrostatic interactions. In a single molecule, the Cl - anion is also engaged in a slightly longer hydrogen bond, O-H...Cl - =2.948-3.019 Angst, but only in one type of intramolecular electrostatic interaction. The optimized bond lengths and bond angles at the MP2 and B3LYP levels of theory are in good agreement with the X-ray data, except conformation of the COOH group, which is cis (syn) in the crystal and trans (anti) in the single molecule. The probable assignments for the experimental solid state vibrational spectra of TRGH.Cl and TRGD.Cl based on the calculated MP2/cc-pVDZ frequencies and intensities were made. The effect of quaternization of nicotinic acid, its salt and amide on chemical shifts of the ring protons and carbons is analyzed

  19. Synthesis, crystal structure, and vibrational spectra of the anhydrous lithium dicyanamide Li[N(CN){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Reckeweg, Olaf [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); DiSalvo, Francis J. [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Schulz, Armin [Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, 70569 Stuttgart (Germany); Blaschkowski, Bjoern; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); Jagiella, Stefan [Institut fuer Physikalische und Theoretische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

    2014-04-15

    Crystals of Li[N(CN){sub 2}] were synthesized from a metathesis reaction of stoichiometric amounts of aqueous solutions of Na[N(CN){sub 2}] and Li{sub 2}[SO{sub 4}] followed by subsequent treatment with ethanol and evaporation of the filtered-off solution at 80 C under normal atmospheric conditions. The single crystals of the title compound are transparent, colorless, and extremly hygroscopic. X-ray structure analysis showed that Li[N(CN){sub 2}] crystallizes in the monoclinic space group P2/c with the cell parameters a = 530.79(8) pm, b = 524.89(9) pm, c = 1149.77(17) pm, β = 101.551(7) , and Z = 4. The crystal structure contains Li{sup +} cations in both tetrahedral and octahedral nitrogen coordination of the boomerang-shaped [N≡C-N-C≡N]{sup -} anions. The vibrational spectra of Li[N(CN){sub 2}] are reported as well, together with ab initio calculations for geometry and harmonic frequencies of the free dicyanamide anion. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Calculating vibrational spectra with sum of product basis functions without storing full-dimensional vectors or matrices.

    Science.gov (United States)

    Leclerc, Arnaud; Carrington, Tucker

    2014-05-07

    We propose an iterative method for computing vibrational spectra that significantly reduces the memory cost of calculations. It uses a direct product primitive basis, but does not require storing vectors with as many components as there are product basis functions. Wavefunctions are represented in a basis each of whose functions is a sum of products (SOP) and the factorizable structure of the Hamiltonian is exploited. If the factors of the SOP basis functions are properly chosen, wavefunctions are linear combinations of a small number of SOP basis functions. The SOP basis functions are generated using a shifted block power method. The factors are refined with a rank reduction algorithm to cap the number of terms in a SOP basis function. The ideas are tested on a 20-D model Hamiltonian and a realistic CH3CN (12 dimensional) potential. For the 20-D problem, to use a standard direct product iterative approach one would need to store vectors with about 10(20) components and would hence require about 8 × 10(11) GB. With the approach of this paper only 1 GB of memory is necessary. Results for CH3CN agree well with those of a previous calculation on the same potential.

  1. Analysis of discrete and continuous laser induced fluorescence spectra of the A 1Σsub(u)+-X 1Σsub(g)+ band system of Sr2

    International Nuclear Information System (INIS)

    Gerber, G.; Moeller, R.

    1982-01-01

    Laser induced fluorescence spectra of the gaseous Sr 2 excimer molecule have been measured. The spectra contain discrete molecular fluorescence series, regularly modulated continuous fluorescence and an unstructured continuum. Analysis of the molecular line spectra yields for the first time Dunham coefficients for the X 1 Σsub(g) + ground state and the A 1 Σsub(u) + excited state. Using the intensity distribution of the modulated continuum which is associated with bound-free transitions the repulsive potential of the ground state up to 3000 cm -1 above the dissociation limit has been determined. The unstructured continuum can be analyzed as due to two types of continuous fluorescence. The dissociation energy of Sr 2 has been determined to Dsub(e)(X) = 965 +- 45 cm -1 . (Auth.)

  2. Analysis of discrete and continuous laser induced fluorescence spectra of the A 1μ+sub(u) - X 1μ+sub(g) band system of SR2

    International Nuclear Information System (INIS)

    Gerber, G.; Moeller, R.

    1982-01-01

    Laser induced fluorescence spectra of the gaseous Sr 2 excimer molecule have been measured. The spectra contain discrete molecular fluorescence series, regularly modulated continuous fluorescence and an unstructured continuum. Analysis of the molecular line spectra yields for the first time Dunham coefficients for the X 1 μ + sub(g) ground state and the A 1 μ + sub(u) excited state. Using the intensity distribution of the modulated continuum which is associated with bound-free transitions the repulsive potential of the ground state up to 3000 cm - 1 above the dissociation limit has been determined. The unstructured continuum can be analyzed as due to two types of continuous fluorescence. The dissociation energy of Sr 2 has been determined to Dsub(e) (X) = 965 +- 45 cm - 1 . (Author)

  3. Neural-network analysis of the vibrational spectra of N-acetyl L-alanyl N '-methyl amide conformational states

    DEFF Research Database (Denmark)

    Bohr, Henrik; Frimand, Kenneth; Jalkanen, Karl J.

    2001-01-01

    Density-functional theory (DFT) calculations utilizing the Becke 3LYP hybrid functional have been carried out for N-acetyl L-alanine N'-methylamide and examined with respect to the effect of water on the structure, the vibrational frequencies, vibrational absorption (VA), vibrational circular dic...

  4. The photodissociation and reaction dynamics of vibrationally excited molecules

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

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

  5. Fluorescence spectral correlation spectroscopy (FSCS) for probes with highly overlapping emission spectra

    Czech Academy of Sciences Publication Activity Database

    Benda, A.; Kapusta, Peter; Hof, Martin; Gaus, K.

    2014-01-01

    Roč. 22, č. 3 (2014), s. 2973-2988 ISSN 1094-4087 R&D Projects: GA AV ČR KJB400400904; GA ČR GBP208/12/G016 Institutional support: RVO:61388955 Keywords : spectroscopy * fluorescence and luminiscence * confocal microscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.488, year: 2014

  6. Laser resonant ionization spectroscopy and laser-induced resonant fluorescence spectra of samarium atom

    International Nuclear Information System (INIS)

    Jin, Changtai

    1995-01-01

    We have measured new high-lying levels of Sm atom by two-colour resonant photoionisation spectroscopy; we have observed the isotope shifts of Sm atom by laser-induced resonant fluorescence spectroscopy; the lifetime of eight low-lying levels of Sm atom were measured by using pulsed laser-Boxcar technique in atomic beam.

  7. Vibrational assignments for the Raman and the phosphorescence spectra of 9,10-anthraquinone and 9,10-anthraquinone-d81

    International Nuclear Information System (INIS)

    Lehmann, K.K.; Smolarek, J.; Khalil, O.S.; Goodman, L.

    1979-01-01

    The Raman spectra of 9,10-anthraquinone (AQ) and 9,10-anthraquinone-d/sub 8/ are examined. Raman band assignments are made from this data and from a published normal coordinate analysis. The Raman spectra of AQ at 5K is reported and vibrational assignments for the phosphorescence spectra of AQ in n-hexane at 4.2 K are reexamined in light of new 3 B 1 /sub g/ → 1 A/sub g/ phosphorescence data. Contrary to previous work from this laboratory, it is concluded that although higher order vibronic interactions may be operative between the two closely spaced 3 A/sub u/- 3 B 1 /sub g/ electronic states, these interactions are not manifested in the phosphorescence spectra of AQ in n-hexane at 4.2 K

  8. Multi-Photon Absorption Spectra: A Comparison Between Transmittance Change and Fluorescence Methods

    Science.gov (United States)

    2015-05-21

    AFRL-OSR-VA-TR-2015-0134 multi-photon absorption spectra Cleber Mendonca INSTITUTO DE FISICA DE SAO CARLOS Final Report 05/21/2015 DISTRIBUTION A...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Instituto de Fisica de Sao Carlos - Universidade de Sao Paulo Av

  9. Fluorescence of Bacteria, Pollens, and Naturally Occurring Airborne Particles: Excitation/Emission Spectra

    Science.gov (United States)

    2009-02-01

    35 Figure 29. EEM spectra of kaolin particles, dry...Warrington, PA. Glass beads were obtained from Peirce Chemical Co., Rockford, IL. Kaolin particles were obtained from Particle Information Services...solution concentration of 1 mg/ml. The samples were vortexed and pipetted vigorously to disperse aggregates. Stock bacteria solutions were diluted to a

  10. Molecular structure and vibrational spectra of MHal3 (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I): ab initio calculations by the CISD+Q method

    International Nuclear Information System (INIS)

    Solomonik, V.G.; Marochko, O.Yu.

    2000-01-01

    Structure and vibrational spectra of MHal 3 molecules (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I) are studied by the CISD+Q method. It is ascertained that equilibrium configuration of nuclei in all the molecules, except LaF 3 , is plane (D 3h symmetry), while that of LaF 3 molecule - pyramidal (C 3c symmetry). Results of the calculations are compared with previously published experimental data. Band reference in IR spectra of ScBr 3 , YF 3 and YCl 3 molecules has been corrected [ru

  11. Comparison of the performance of different DFT methods in the calculations of the molecular structure and vibration spectra of serotonin (5-hydroxytryptamine, 5-HT)

    Science.gov (United States)

    Yang, Yue; Gao, Hongwei

    2012-04-01

    Serotonin (5-hydroxytryptamine, 5-HT) is a monoamine neurotransmitter which plays an important role in treating acute or clinical stress. The comparative performance of different density functional theory (DFT) methods at various basis sets in predicting the molecular structure and vibration spectra of serotonin was reported. The calculation results of different methods including mPW1PW91, HCTH, SVWN, PBEPBE, B3PW91 and B3LYP with various basis sets including LANL2DZ, SDD, LANL2MB, 6-31G, 6-311++G and 6-311+G* were compared with the experimental data. It is remarkable that the SVWN/6-311++G and SVWN/6-311+G* levels afford the best quality to predict the structure of serotonin. The results also indicate that PBEPBE/LANL2DZ level show better performance in the vibration spectra prediction of serotonin than other DFT methods.

  12. Emission spectra of the species ablated from a solid target submerged in liquid: vibrational temperature of C2 molecules in water-confined geometry

    International Nuclear Information System (INIS)

    Sakka, Tetsuo; Saito, Kotaro; Ogata, Yukio H.

    2002-01-01

    Emission spectra of C 2 molecules produced at the water-graphite interface by pulsed laser irradiation were obtained at various delay times from the irradiation. Vibrational temperature was determined by the Boltzmann plot based on the vibrational bands in Δν=-1 branch of the Swan system. The results show that it was ca. 5000 K and did not change significantly with the delay time. With increasing the delay time up to ca. 500 ns the signal from the Swan band disappeared before the decrease of the vibrational temperature. The results were explained by the formation of a gas cavity and its collapse at several hundreds of nanoseconds from the laser pulse

  13. Solvent polarity scale on the fluorescence spectra of a dansyl monomer copolymerizable in aqueous media

    Science.gov (United States)

    Ren, Biye; Gao, Feng; Tong, Zhen; Yan, Yu

    1999-06-01

    A copolymerizable fluorescent monomer N-[2-[[[5-(N,N-dimethylamino)-1-naphthalenyl]sulfonyl]-amino]ethyl]-2-propenamide (DANSAEP) was synthesized, which exhibits dual fluorescence due to the twisted intramolecular charge transfer in the excited state. The emission maximum λem shifts from 463.3 nm in n-hexane to 530.0 nm in water, showing solvent polarity dependence. The relations between λem and the conventional solvent polarity parameters ET(30) or Z are linear, dividing solvents into protic and aprotic groups. Kamlet's linear solvation energy relationship gives a good description for λem as a solvent polarity scale. The increment of dipole moment Δ μ at the excited state was estimated as 5.09 D with the solvatochromic analysis.

  14. High-resolution spectroscopy in superfluid helium droplets. Investigation of vibrational fine structures in electronic spectra of phthalocyanine and porphyrin derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Ricarda Eva Friederike Elisabeth

    2011-03-22

    Since a considerably large variety of substituted compounds is commercially available and the electronic excitation spectra fit well into the spectral range covered by the continuous wave dye laser used for this study several porphyrin and phthalocyanine derivatives substituted with different types and numbers of alkyl and aryl groups were chosen as molecular probes. Recording fluorescence excitation and dispersed emission spectra revealed exclusively sharp transitions for all species. A change of the molecule's electrostatic moments, primarily and most effectively, a change of the molecular dipole moment regarding both magnitude and orientation, was identified as the main contribution for line broadening effects. Apart from the sharp lines presented in their fluorescence excitation spectra, the phthalocyanine derivatives investigated for this study, namely chloro-aluminium-phthalocyanine (AlClPc) and tetra-tertbutyl-phthalocyanine (TTBPc), exhibited more than one emission spectrum.

  15. High-resolution spectroscopy in superfluid helium droplets. Investigation of vibrational fine structures in electronic spectra of phthalocyanine and porphyrin derivatives

    International Nuclear Information System (INIS)

    Riechers, Ricarda Eva Friederike Elisabeth

    2011-01-01

    Since a considerably large variety of substituted compounds is commercially available and the electronic excitation spectra fit well into the spectral range covered by the continuous wave dye laser used for this study several porphyrin and phthalocyanine derivatives substituted with different types and numbers of alkyl and aryl groups were chosen as molecular probes. Recording fluorescence excitation and dispersed emission spectra revealed exclusively sharp transitions for all species. A change of the molecule's electrostatic moments, primarily and most effectively, a change of the molecular dipole moment regarding both magnitude and orientation, was identified as the main contribution for line broadening effects. Apart from the sharp lines presented in their fluorescence excitation spectra, the phthalocyanine derivatives investigated for this study, namely chloro-aluminium-phthalocyanine (AlClPc) and tetra-tertbutyl-phthalocyanine (TTBPc), exhibited more than one emission spectrum.

  16. Analysis of kiwi fruit (Accented deliciosa) by energy dispersive X-ray fluorescence spectra

    International Nuclear Information System (INIS)

    Oliveira, Ana Claudia S.; Oliveira, Marcia L. de; Silva, Lucia C.A.S.; Arthur, Valter; Almeida, Eduardo

    2011-01-01

    The search for a healthy life has led consumers to eat fruits and vegetables in place of manufactured products, however, the demand for minimally processed products has evolved rapidly. The kiwi has at least eight nutrients beneficial to health: calcium, magnesium, manganese, phosphorus, iron, potassium, sodium and has also high vitamin C, which has wide acceptance in consumer markets. Energy dispersive spectroscopy X-ray (EDX) is the analytical technique used for elemental analysis or chemical characterization of a sample. It is a variant of fluorescence spectroscopy X-ray based on the sample through an investigation of interactions between electromagnetic radiation and matter, analyzing X-rays emitted by matter in response to being struck by charged particles. The aim of this study were to determine potassium, calcium, iron and bromine (K, Ca, Fe and Br, respectively) present in kiwifruit using the technique of fluorescence X-ray energy dispersive (EDXRF). Kiwifruit were peeled, washed and cut into slices and freeze-dried. After drying the sample was held digestion and subsequent reading of the same equipment in the X-ray fluorescence energy dispersive (EDXRF). The results indicated that the contents of potassium, calcium, iron and bromine are present in kiwifruit as expected when compared to Brazilian Table of Food Composition. (author)

  17. The fluorescence action spectra of some saturated hydrocarbon liquids for excitation energies above and below their ionization thresholds

    International Nuclear Information System (INIS)

    Ostafin, A.E.; Lipsky, S.

    1993-01-01

    Fluorescence action spectra have been obtained for the neat liquids, cis-decalin, trans-decalin, bicyclohexyl, cyclohexane, methylcyclohexane, isobutylcyclohexane, 2,3,4-trimethylpentane, 2,3-dimethylbutane, 3-methylhexane, 3-methylpentane, n-decane, n-dodecane, and n-pentadecane at excitation energies, ε, ranging from their absorption onsets (at ca. 7 eV) to 10.3 eV. For all compounds, with the exception of cis-decalin, the fluorescence quantum yield is observed to monotonically decline with increasing ε, reaching a minimum value at an energy, ε m (a few tenths of an eV above the liquid phase ionization threshold, ε l ) followed by a slow increase. In the case of cis-decalin, the fluorescence quantum yield remains constant over the entire range of excitation energies studied, permitting its use as a quantum counter replacing the standard sodium salicylate, at least over a spectral range from 185 to 120 nm. The recovery of the fluorescence quantum yield for ε>ε m is attributed to an increasing probability for electron ejection followed by e - +RH + geminate recombination, to produce an excited state of RH with energy less than ε l . From a simple analysis of the action spectrum, a lower bound estimate of the electron ejection probability, φ ± , is obtained as a function of ε. In the case of cyclohexane, where φ ± has been obtained by other techniques at ε congruent 10 eV, the lower bound estimate agrees with the experimental value. From this agreement, arguments are presented to make plausible the conjecture that in all these liquids, the initially produced e - +RH + geminate ion pair first rapidly internally converts to an ion-pair state ca

  18. Vibrational spectra (FT-IR, FT-Raman), frontier molecular orbital, first hyperpolarizability, NBO analysis and thermodynamics properties of Piroxicam by HF and DFT methods

    Science.gov (United States)

    Suresh, S.; Gunasekaran, S.; Srinivasan, S.

    2015-03-01

    The solid phase FT-IR and FT-Raman spectra of 4-Hydroxy-2-methyl-N-(2-pyridinyl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (Piroxicam) have been recorded in the region 4000-400 and 4000-100 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of piroxicam in the ground state have been calculated by Hartree-Fock (HF) and density functional theory (DFT) methods using 6-311++G(d,p) basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimental obtained by FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of the title compound has been made on the basis of the calculated potential energy distribution (PED). The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MESP) are also performed. The linear polarizability (α) and the first order hyper polarizability (β) values of the title compound have been computed. The molecular stability arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis.

  19. The vibrational spectra of N-phenylpyrrole in the gas phase, in argon matrices and in single crystals

    International Nuclear Information System (INIS)

    Schweke, D.; Brauer, B.; Gerber, R.B.; Haas, Y.

    2007-01-01

    The infrared spectrum of N-phenylpyrrole (PP) was measured in the gas phase and in an argon matrix, and the Raman spectrum was obtained in a single crystal. The measured matrix shifts are found to be small: many bands are not split, and the shifts from the gas phase values are less than 1%. Splitting to two sub-bands is observed for some bands, indicating the presence of two major trapping sites, in agreement with previous predictions. The spectra are analyzed with the help of harmonic calculations on the free molecule and on its adduct with one or two argon atoms, and anharmonic frequency calculations on the free molecule. Harmonic frequencies were obtained at the MP2/cc-pVDZ and DFT-B3LYP/cc-pVDZ levels. Anharmonic frequencies were obtained by the correlation-corrected vibrational self-consistent field (CC-VSCF) method with a variant of the PM3 semiempirical electronic structure method, calibrated for much improved spectroscopic accuracy. The potential surfaces used in the CC-VSCF calculation obtained by adjusting standard PM3 surfaces so that they provide harmonic frequencies that are comparable to those obtained at the DFT-B3LYP/cc-pVDZ level. Agreement between the experimental and theoretical results is in general very good, allowing the assignments of most bands. The harmonic frequency calculations of PP-Ar clusters, at the MP2/cc-pVDZ level show that the environment can greatly affect the intensities of some of the transitions, which is in accord with experiment

  20. Quantification of two forms of green sulfur bacteria in their natural habitat using bacteriochlorophyll fluorescence spectra

    Science.gov (United States)

    Kharcheva, Anastasia V.; Zhiltsova, Anna A.; Lunina, Olga N.; Savvichev, Alexander S.; Patsaeva, Svetlana V.

    2016-04-01

    Detection of phototropic organisms in their natural habitat using optical instruments operating under water is urgently needed for many tasks of ecological monitoring. While fluorescence methods are widely applied nowadays to detect and characterize phytoplankton communities, the techniques for detection and recognition of anoxygenic phototrophs are considered challenging. Differentiation of the forms of anoxygenic green sulfur bacteria in natural water using spectral techniques remains problematic. Green sulfur bacteria could be found in two forms, green-colored (containing BChl d in pigment compound) and brown-colored (containing BChl e), have the special ecological niche in such reservoirs. Separate determination of these microorganisms by spectral methods is complicated because of similarity of spectral characteristics of their pigments. We describe the novel technique of quantification of two forms of green sulfur bacteria directly in water using bacteriochlorophyll fluorescence without pigment extraction. This technique is noninvasive and could be applied in remote mode in the water bodies with restricted water circulation to determine simultaneously concentrations of two forms of green sulfur bacteria in their natural habitat.

  1. Interfacial adhesion of nanoparticles in polymer blends by intrinsic fluorescence spectra

    Directory of Open Access Journals (Sweden)

    2011-09-01

    Full Text Available Intrinsic fluorescence was applied to quantitatively describe the interfacial adhesion of nanoparticles in polystyrene/poly(vinyl methyl ether (PS/PVME blends. Due to the aggregation of aromatic rings on PS chains, the temperature dependence of excimer fluorescence intensity (I324 showed the high sensitivity to the phase separation process. Consistent with Ginzburg thermodynamic model, it was found that the addition of spherical hydrophilic nanoparticles shifted the phase separation temperature to higher temperatures due to the aggregation of silica into PVME chains leading to the free energy reduction and slowing down the phase separation dynamics. A certain composition of polymer blend, i.e. 2/8, was focused on to shed light on the dynamic of spinodal decomposition (SD phase separation by using decomposition reaction model. It was shown that the addition of nanoparticles to polymer blends resulted in the deviation of linear relationship between the initial SD phase separation rate (Rp0 and thermodynamic driving force (ΔfSD. Besides, for PS/PVME (2/8 with 2 vol% silica nanoparticles, the apparent activation energy of phase separation (Ea was 196.61 kJ/mol, which was higher than that of neat PS/PVME (2/8 blend (Ea = 173.68 kJ/mol, which strongly confirmed the interfacial adhesion effect of silica nanoparticles as compatibilizers.

  2. A disordered polaron model for polarized fluorescence excitation spectra of LH1 and LH2 bacteriochlorophyll antenna aggregates

    International Nuclear Information System (INIS)

    Trinkunas, Gediminas; Freiberg, Arvi

    2006-01-01

    Excitonic polarons in antenna complexes are subject to static lattice disorder. A model has been developed to analyze polarized fluorescence excitation spectra of circular light-harvesting complexes from purple photosynthetic bacteria containing bacteriochlorophyll as the main photoactive pigment that includes both diagonal (energetic) and off-diagonal (structural) disorders. Essential differences of disorder realizations seem to exist between the core LH1 and peripheral LH2 complexes from the bacterium Rhodobacter sphaeroides. The disorder in LH1 appears to be dominated by the structural disorder, while that in LH2, by energetic one. These differences may be due to relatively bigger size of the LH1 complex and, consequently, with its enhanced structural flexibility

  3. Vibrational energy flow through the green fluorescent protein-water interface: communication maps and thermal boundary conductance.

    Science.gov (United States)

    Xu, Yao; Leitner, David M

    2014-07-17

    We calculate communication maps for green fluorescent protein (GFP) to elucidate energy transfer pathways between the chromophore and other parts of the protein in the ground and excited state. The approach locates energy transport channels from the chromophore to remote regions of the protein via residues and water molecules that hydrogen bond to the chromophore. We calculate the thermal boundary conductance between GFP and water over a wide range of temperature and find that the interface between the protein and the cluster of water molecules in the β-barrel poses negligible resistance to thermal flow, consistent with facile vibrational energy transfer from the chromophore to the β-barrel waters observed in the communication maps.

  4. Interactions of glutamine dipeptides with sodium dodecyl sulfate in aqueous solution measured by volume, conductivity, and fluorescence spectra

    Energy Technology Data Exchange (ETDEWEB)

    Yan Zhenning, E-mail: yanzzn@zzu.edu.cn [Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001 (China); Sun Ximeng; Li Weiwei; Li Yu [Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001 (China); Wang Jianji [Department of Chemistry, Henan Normal University, Xinxiang, Henan 453007 (China)

    2011-10-15

    Highlights: > Ion-ion and ion-polar group interactions are dominant interactions. > The SDS addition and temperature increase cause a dehydration effect on dipeptides. > The addition of dipeptide in water decreases the c{sub cmc} of SDS. > Enthalpy-entropy compensation takes place during micellization. > Micelle aggregation number was decreased by addition of glutamine dipeptides. - Abstract: Densities, conductivities, and fluorescence spectra of {l_brace}sodium dodecyl sulfate (SDS) + glutamine dipeptide + water{r_brace} mixtures were measured as a function of temperature. The density data have been utilized to calculate apparent molar volumes, standard partial molar volumes (V{sub 2,{phi}}{sup o}), standard partial molar volumes of transfer from water to aqueous SDS solutions ({Delta}{sub t}V{sup o}), the hydration number, partial molar expansibility (E{sub {phi}}{sup o}), and Hepler's constant of glutamine dipeptides. The critical micellar concentration (c{sub cmc}) and the degree of counterion dissociation of SDS micelles obtained from electrical conductivity data have been estimated at various concentrations of glutamine dipeptide. Thermodynamic parameters of micellization of SDS in aqueous dipeptide solutions have been determined from c{sub cmc} values and an enthalpy-entropy compensation effect was observed for the ternary systems. The pyrene fluorescence spectra were used to study the change of micropolarity produced by the interaction of SDS with glutamine dipeptide, and the aggregation behavior of SDS. The results have been interpreted in terms of solute-solvent interactions and structural changes in the mixed solutions.

  5. Analysis of chlorophyll fluorescence spectra for the monitoring of Cd toxicity in a bio-energy crop (Jatropha curcas).

    Science.gov (United States)

    Marques, Marise Conceição; do Nascimento, Clístenes Williams Araújo

    2013-10-05

    The vegetation of metal-contaminated soils using non-edible crops can be a safe and economical technique for Cd immobilization and the remediation of contaminated sites. Jatropha (Jatropha curcas L.) exhibits a relative tolerance to heavy metals and potential for biofuel production. The study was performed to monitor the Cd-induced alterations in jatropha plants by X-ray chlorophyll fluorescence. The Cd effects on photosynthetic pigments, the mineral composition of plants, defense enzyme activity and soluble proteins were also studied. Plants were grown for 20days in a nutrient solution with five Cd contents: 5, 10, 20, 30 and 40μmolL(-1); a control with no Cd addition was also monitored. The analysis of the chlorophyll fluorescence spectra allowed detecting alterations caused by Cd toxicity in the jatropha plants. The mineral composition of the plants was affected by the Cd doses; however, the Fe and Mg contents were not significantly reduced, which most likely improved the effects on the contents of the photosynthetic pigments. Because of its relative tolerance to Cd, Jatropha curcas may be a promising species to revegetate Cd-contaminated sites. Considering the long period needed to phytoremediate soils, the combination of remediation with bioenergy production could be an attractive option. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. A novel quantitative analysis method of three-dimensional fluorescence spectra for vegetable oils contents in edible blend oil

    Science.gov (United States)

    Xu, Jing; Wang, Yu-Tian; Liu, Xiao-Fei

    2015-04-01

    Edible blend oil is a mixture of vegetable oils. Eligible blend oil can meet the daily need of two essential fatty acids for human to achieve the balanced nutrition. Each vegetable oil has its different composition, so vegetable oils contents in edible blend oil determine nutritional components in blend oil. A high-precision quantitative analysis method to detect the vegetable oils contents in blend oil is necessary to ensure balanced nutrition for human being. Three-dimensional fluorescence technique is high selectivity, high sensitivity, and high-efficiency. Efficiency extraction and full use of information in tree-dimensional fluorescence spectra will improve the accuracy of the measurement. A novel quantitative analysis is proposed based on Quasi-Monte-Carlo integral to improve the measurement sensitivity and reduce the random error. Partial least squares method is used to solve nonlinear equations to avoid the effect of multicollinearity. The recovery rates of blend oil mixed by peanut oil, soybean oil and sunflower are calculated to verify the accuracy of the method, which are increased, compared the linear method used commonly for component concentration measurement.

  7. Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

    Science.gov (United States)

    Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

    2014-01-01

    The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3·5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm−1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe2+/[Fe2+ + Fe3+] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

  8. Fundamental quantification procedure for total reflection X-ray fluorescence spectra analysis and elements determination

    International Nuclear Information System (INIS)

    Wegrzynek, D.; Holynska, B.

    1997-01-01

    A method for the determination of the concentrations of elements in particulate-like samples measured in total reflection geometry is proposed. In the proposed method the fundamental parameters are utilized for calculating the sensitivities of elements and an internal standard is used to account for the unknown mass per unit area of a sample and geometrical constant of the spectrometer. The modification of the primary excitation spectrum on its way to a sample has been taken into consideration. The concentrations of the elements to be determined are calculated simultaneously with the spectra deconvolution procedure. In the process of quantitative analysis the intensities of all X-ray peaks corresponding to K and L-series lines present in the analyzed spectrum are taken into account. (Author)

  9. Non-equilibrium effects evidenced by vibrational spectra during the coil-to-globule transition in poly(N-isopropylacrylamide) subjected to an ultrafast heating-cooling cycle.

    Science.gov (United States)

    Deshmukh, Sanket A; Kamath, Ganesh; Suthar, Kamlesh J; Mancini, Derrick C; Sankaranarayanan, Subramanian K R S

    2014-03-14

    Molecular dynamics simulations in conjunction with finite element calculations are used to explore the conformational dynamics of a thermo-sensitive oligomer, namely poly(N-isopropylacrylamide) (PNIPAM), subjected to an ultra-fast heating-cooling cycle. Finite element (FE) calculations were used to predict the temperature profile resulting from laser-induced heating of the polymer-aqueous system. The heating rate (∼0.6 K ps(-1)) deduced from FE calculations was used to heat an aqueous solution of PNIPAM consisting of 30 monomeric units (30-mer) from 285 K to 315 K. Non-equilibrium effects arising from the ultra-fast heating-cooling cycle results in a hysteresis during the coil-to-globule transition. The corresponding atomic scale conformations were characterized by monitoring the changes in the vibrational spectra, which provided a reliable metric to study the coil-to-globule transition in PNIPAM and vice-versa across the LCST. The vibrational spectra of bonds involving atoms from the oligomer backbone and the various side-groups (amide I, amide II, and the isopropyl group of PNIPAM) of the oligomers were analyzed to study the conformational changes in the oligomer corresponding to the observed hysteresis. The differences in the vibrational spectra calculated at various temperatures during heating and cooling cycles were used to understand the coil-to-globule and globule-to-coil transitions in the PNIPAM oligomer and identify the changes in the relative interactions between various atoms in the backbone and in the side groups of the oligomer with water. The shifts in the computed vibrational spectral peaks and the changes in the intensity of peaks for the different regions of PNIPAM, seen across the LCST during the heating cycle, are in good agreement with previous experimental studies. The changes in the radius of gyration (Rg) and vibrational spectra for amide I and amide II regions of PNIPAM suggest a clear coil-to-globule transition at ∼301 K during the

  10. A study of vibrational spectra and investigations of charge transfer and chemical bonding features of 2-chloro benzimidazole based on DFT computations

    Science.gov (United States)

    Muthunatesan, S.; Ragavendran, V.

    2015-01-01

    Benzimidazoles are bicyclic heteroatomic molecules. Polycyclic heteroatomic molecules have extensive coupling of different modes leading to strong coupling of force constants associated with the various chemical bonds of the molecules. To carry out a detailed vibrational spectroscopic analysis of such a bicyclic heteroatomic molecule, FT-IR and FT-Raman spectra of 2-chloro benzimidazole (CBZ) have been recorded in the condensed phase. Density Functional Theory calculations in the B3LYP/6-31G* level have been carried out to determine the optimized geometry and vibrational frequencies. In order to obtain a close agreement between theoretical and observed frequencies and hence to perform a reliable assignment, the theoretical DFT force field was transformed from Cartesian to local symmetry co-ordinates and then scaled empirically using SQM methodology. The SQM treatment resulted in a RMS deviation of 9.4 cm-1. For visual comparison, the observed and calculated spectra are presented on a common wavenumber scale. From the NBO analysis, the electron density (ED) charge transfers in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated Homo and Lumo energies show that charge transfer occurs within the molecule. The results obtained from the vibrational, NBO and HOMO-LUMO analyses have been properly tabulated.

  11. Direct on-strip analysis of size- and time-resolved aerosol impactor samples using laser induced fluorescence spectra excited at 263 and 351 nm

    International Nuclear Information System (INIS)

    Wang, Chuji; Pan, Yong-Le; James, Deryck; Wetmore, Alan E.; Redding, Brandon

    2014-01-01

    Highlights: • A dual wavelength UV-LIF spectra-rotating drum impactor (RDI) technique was developed. • The technique was demonstrated by direct on-strip analysis of size- and time-resolved LIF spectra of atmospheric aerosol particles. • More than 2000 LIF spectra of atmospheric aerosol particles collected over three weeks in Djibouti were obtained and assigned to various fluorescence clusters. • The LIF spectra showed size- and time-sensitivity behavior with a time resolution of 3.6 h. - Abstract: We report a novel atmospheric aerosol characterization technique, in which dual wavelength UV laser induced fluorescence (LIF) spectrometry marries an eight-stage rotating drum impactor (RDI), namely UV-LIF-RDI, to achieve size- and time-resolved analysis of aerosol particles on-strip. The UV-LIF-RDI technique measured LIF spectra via direct laser beam illumination onto the particles that were impacted on a RDI strip with a spatial resolution of 1.2 mm, equivalent to an averaged time resolution in the aerosol sampling of 3.6 h. Excited by a 263 nm or 351 nm laser, more than 2000 LIF spectra within a 3-week aerosol collection time period were obtained from the eight individual RDI strips that collected particles in eight different sizes ranging from 0.09 to 10 μm in Djibouti. Based on the known fluorescence database from atmospheric aerosols in the US, the LIF spectra obtained from the Djibouti aerosol samples were found to be dominated by fluorescence clusters 2, 5, and 8 (peaked at 330, 370, and 475 nm) when excited at 263 nm and by fluorescence clusters 1, 2, 5, and 6 (peaked at 390 and 460 nm) when excited at 351 nm. Size- and time-dependent variations of the fluorescence spectra revealed some size and time evolution behavior of organic and biological aerosols from the atmosphere in Djibouti. Moreover, this analytical technique could locate the possible sources and chemical compositions contributing to these fluorescence clusters. Advantages, limitations, and

  12. Direct on-strip analysis of size- and time-resolved aerosol impactor samples using laser induced fluorescence spectra excited at 263 and 351 nm

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chuji [U.S. Army Research Laboratory, Adelphi, MD 20783 (United States); Mississippi State University, Starkville, MS, 39759 (United States); Pan, Yong-Le, E-mail: yongle.pan.civ@mail.mil [U.S. Army Research Laboratory, Adelphi, MD 20783 (United States); James, Deryck; Wetmore, Alan E. [U.S. Army Research Laboratory, Adelphi, MD 20783 (United States); Redding, Brandon [Yale University, New Haven, CT 06510 (United States)

    2014-04-01

    Highlights: • A dual wavelength UV-LIF spectra-rotating drum impactor (RDI) technique was developed. • The technique was demonstrated by direct on-strip analysis of size- and time-resolved LIF spectra of atmospheric aerosol particles. • More than 2000 LIF spectra of atmospheric aerosol particles collected over three weeks in Djibouti were obtained and assigned to various fluorescence clusters. • The LIF spectra showed size- and time-sensitivity behavior with a time resolution of 3.6 h. - Abstract: We report a novel atmospheric aerosol characterization technique, in which dual wavelength UV laser induced fluorescence (LIF) spectrometry marries an eight-stage rotating drum impactor (RDI), namely UV-LIF-RDI, to achieve size- and time-resolved analysis of aerosol particles on-strip. The UV-LIF-RDI technique measured LIF spectra via direct laser beam illumination onto the particles that were impacted on a RDI strip with a spatial resolution of 1.2 mm, equivalent to an averaged time resolution in the aerosol sampling of 3.6 h. Excited by a 263 nm or 351 nm laser, more than 2000 LIF spectra within a 3-week aerosol collection time period were obtained from the eight individual RDI strips that collected particles in eight different sizes ranging from 0.09 to 10 μm in Djibouti. Based on the known fluorescence database from atmospheric aerosols in the US, the LIF spectra obtained from the Djibouti aerosol samples were found to be dominated by fluorescence clusters 2, 5, and 8 (peaked at 330, 370, and 475 nm) when excited at 263 nm and by fluorescence clusters 1, 2, 5, and 6 (peaked at 390 and 460 nm) when excited at 351 nm. Size- and time-dependent variations of the fluorescence spectra revealed some size and time evolution behavior of organic and biological aerosols from the atmosphere in Djibouti. Moreover, this analytical technique could locate the possible sources and chemical compositions contributing to these fluorescence clusters. Advantages, limitations, and

  13. Identification of the pigment responsible for the blue fluorescence band in the laser induced fluorescence (LIF) spectra of green plants, and the potential use of this band in remotely estimating rates of photosynthesis

    International Nuclear Information System (INIS)

    Chappelle, E.W.; McMurtrey, J.E. III; Kim, M.S.

    1991-01-01

    The laser-induced fluorescence (LIF) of vegetation is being investigated in this laboratory for use as a technique for the remote detection of the effects of environmental stress upon vegetation, as well as for plant identification. The fluorescence band with a maximum at 440 nm, in conjunction with the chlorophyll bands with maxima at 685 and 740 nm, has been found to be a critical band in the development of algorithms for detecting stress, and identifying plant types. The identification of the plant constituent responsible for this band is vital to understanding the mechanism underlying its fluorescence changes in response to environmental and physiological changes. The identification was achieved as follows: The laser induced fluorescence (LIF) spectra of pure plant pigments were determined. Fluorescence bands with maxima at 420 nm, 440 nm, 490 nm, and 525 nm were observed for vitamin K 1 , reduced nicotinamide adenine dinucleotide (NADPH), beta-carotene, and riboflavin, respectively. The LIF spectra of water extracts and acetone extracts of clover leaves were also measured. It was found that the blue fluorescence band was associated with the water extract. NADPH which is a water-soluble compound, and the water extract of clover had no fluorescence after oxidation by potassium ferricyanide, while the fluorescence of water insoluble vitamin K 1 was unchanged by the oxidizing agent. It was also found that the absorption maximum of NADPH was the same as the absorption maximum of the aqueous extract of clover. The above findings indicated that the compound responsible for the blue fluorescence at 440 nm is in the reduced state and is water-soluble. It was concluded that NADPH was responsible for the blue fluorescence at 440 nm. The strong linear relationship between the fluorescence at 440 nm and the rate of photosynthesis suggests the possible use of LIF measurements in the remote estimation of photosynthetic rates. (author)

  14. The influence of visible light and inorganic pigments on fluorescence excitation emission spectra of egg-, casein- and collagen-based painting media

    Science.gov (United States)

    Nevin, A.; Anglos, D.; Cather, S.; Burnstock, A.

    2008-07-01

    Spectrofluorimetric analysis of proteinaceous binding media is particularly promising because proteins employed in paintings are often fluorescent and media from different sources have significantly different fluorescence spectral profiles. Protein-based binding media derived from eggs, milk and animal tissue have been used for painting and for conservation, but their analysis using non-destructive techniques is complicated by interferences with pigments, their degradation and their low concentration. Changes in the fluorescence excitation emission spectra of films of binding media following artificial ageing to an equivalent of 50 and 100 years of museum lighting include the reduction of bands ascribed to tyrosine, tryptophan and Maillard reaction products and an increase in fluorescent photodegradation. Fluorescence of naturally aged paint is dependent on the nature of the pigment present and, with egg-based media, in comparison with un-pigmented films, emissions ascribed to amino acids are more pronounced.

  15. Vibration and acoustic frequency spectra for industrial process modeling using selective fusion multi-condition samples and multi-source features

    Science.gov (United States)

    Tang, Jian; Qiao, Junfei; Wu, ZhiWei; Chai, Tianyou; Zhang, Jian; Yu, Wen

    2018-01-01

    Frequency spectral data of mechanical vibration and acoustic signals relate to difficult-to-measure production quality and quantity parameters of complex industrial processes. A selective ensemble (SEN) algorithm can be used to build a soft sensor model of these process parameters by fusing valued information selectively from different perspectives. However, a combination of several optimized ensemble sub-models with SEN cannot guarantee the best prediction model. In this study, we use several techniques to construct mechanical vibration and acoustic frequency spectra of a data-driven industrial process parameter model based on selective fusion multi-condition samples and multi-source features. Multi-layer SEN (MLSEN) strategy is used to simulate the domain expert cognitive process. Genetic algorithm and kernel partial least squares are used to construct the inside-layer SEN sub-model based on each mechanical vibration and acoustic frequency spectral feature subset. Branch-and-bound and adaptive weighted fusion algorithms are integrated to select and combine outputs of the inside-layer SEN sub-models. Then, the outside-layer SEN is constructed. Thus, "sub-sampling training examples"-based and "manipulating input features"-based ensemble construction methods are integrated, thereby realizing the selective information fusion process based on multi-condition history samples and multi-source input features. This novel approach is applied to a laboratory-scale ball mill grinding process. A comparison with other methods indicates that the proposed MLSEN approach effectively models mechanical vibration and acoustic signals.

  16. The influence of anharmonic and solvent effects on the theoretical vibrational spectra of the guanine-cytosine base pairs in Watson-Crick and Hoogsteen configurations.

    Science.gov (United States)

    Bende, Attila; Muntean, Cristina M

    2014-03-01

    The theoretical IR and Raman spectra of the guanine-cytosine DNA base pairs in Watson-Crick and Hoogsteen configurations were computed using DFT method with M06-2X meta-hybrid GGA exchange-correlation functional, including the anharmonic corrections and solvent effects. The results for harmonic frequencies and their anharmonic corrections were compared with our previously calculated values obtained with the B3PW91 hybrid GGA functional. Significant differences were obtained for the anharmonic corrections calculated with the two different DFT functionals, especially for the stretching modes, while the corresponding harmonic frequencies did not differ considerable. For the Hoogtseen case the H⁺ vibration between the G-C base pair can be characterized as an asymmetric Duffing oscillator and therefore unrealistic anharmonic corrections for normal modes where this proton vibration is involved have been obtained. The spectral modification due to the anharmonic corrections, solvent effects and the influence of sugar-phosphate group for the Watson-Crick and Hoogsteen base pair configurations, respectively, were also discussed. For the Watson-Crick case also the influence of the stacking interaction on the theoretical IR and Raman spectra was analyzed. Including the anharmonic correction in our normal mode analysis is essential if one wants to obtain correct assignments of the theoretical frequency values as compared with the experimental spectra.

  17. Comparative analysis of the vibrational structure of the absorption spectra of acrolein in the excited ( S 1) electronic state

    Science.gov (United States)

    Koroleva, L. A.; Tyulin, V. I.; Matveev, V. K.; Pentin, Yu. A.

    2012-04-01

    The assignments of absorption bands of the vibrational structure of the UV spectrum are compared with the assignments of bands obtained by the CRDS method in a supersonic jet from the time of laser radiation damping for the trans isomer of acrolein in the excited ( S 1) electronic state. The ν00 trans = 25861 cm-1 values and fundamental frequencies, including torsional vibration frequency, obtained by the two methods were found to coincide in the excited electronic state ( S 1) for this isomer. The assignments of several absorption bands of the vibrational structure of the spectrum obtained by the CRDS method were changed. Changes in the assignment of (0-v') transition bands of the torsional vibration of the trans isomer in the Deslandres table from the ν00 trans trans origin allowed the table to be extended to high quantum numbers v'. The torsional vibration frequencies up to v' = 5 were found to be close to the frequencies found by analyzing the vibrational structure of the UV spectrum and calculated quantum-mechanically. The coincidence of the barrier to internal rotation (the cis-trans transition) in the one-dimensional model with that calculated quantum-mechanically using the two-dimensional model corresponds to a planar structure of the acrolein molecule in the excited ( S 1) electronic state.

  18. Calculation of exact vibrational spectra for P{sub 2}O and CH{sub 2}NH using a phase space wavelet basis

    Energy Technology Data Exchange (ETDEWEB)

    Halverson, Thomas, E-mail: tom.halverson@ttu.edu; Poirier, Bill [Department of Chemistry and Biochemistry and Department of Physics, Texas Tech University, P.O. Box 41061, Lubbock, Texas 79409-1061 (United States)

    2014-05-28

    ‘‘Exact” quantum dynamics calculations of vibrational spectra are performed for two molecular systems of widely varying dimensionality (P{sub 2}O and CH{sub 2}NH), using a momentum-symmetrized Gaussian basis. This basis has been previously shown to defeat exponential scaling of computational cost with system dimensionality. The calculations were performed using the new “SWITCHBLADE” black-box code, which utilizes both dimensionally independent algorithms and massive parallelization to compute very large numbers of eigenstates for any fourth-order force field potential, in a single calculation. For both molecules considered here, many thousands of vibrationally excited states were computed, to at least an “intermediate” level of accuracy (tens of wavenumbers). Future modifications to increase the accuracy to “spectroscopic” levels, along with other potential future improvements of the new code, are also discussed.

  19. The molecular, electronic structures and vibrational spectra of metal-free, N,N'-dideuterio and magnesium tetra-2,3-pyridino-porphyrazines: Density functional calculations.

    Science.gov (United States)

    Liu, Zhongqiang; Zhang, Xianxi; Zhang, Yuexing; Li, Renjie; Jiang, Jianzhuang

    2006-10-01

    A theoretical investigation of the fully optimized geometries and electronic structures of the metal-free (TPdPzH(2)), N,N'-dideuterio (TPdPzD(2)), and magnesium (TPdPzMg) tetra-2,3-pyridino-porphyrazine has been conducted based on density functional theory. The optimized geometries at density functional theory level for these compounds are reported here for the first time. A comparison between the different molecules for the geometry, molecular orbital, and atomic charge is made. The substituent effect of the N atoms on the molecular structures of these compounds is discussed. The IR and Raman spectra for these three compounds have also been calculated at density functional B3LYP level using the 6-31G(d) basis set. Detailed assignments of the NH, NM, and pyridine ring vibrational bands in the IR and Raman spectra have been made based on assistance of animated pictures. The simulated IR spectra of TPdPzH(2) are compared with the experimental absorption spectra, and very good consistency has been found. The isotope effect on the IR and Raman spectra is also discussed.

  20. Classification of Laser Induced Fluorescence Spectra from Normal and Malignant bladder tissues using Learning Vector Quantization Neural Network in Bladder Cancer Diagnosis

    DEFF Research Database (Denmark)

    Karemore, Gopal Raghunath; Mascarenhas, Kim Komal; Patil, Choudhary

    2008-01-01

    In the present work we discuss the potential of recently developed classification algorithm, Learning Vector Quantization (LVQ), for the analysis of Laser Induced Fluorescence (LIF) Spectra, recorded from normal and malignant bladder tissue samples. The algorithm is prototype based and inherently...

  1. Vibrational spectra of halide-water dimers: Insights on ion hydration from full-dimensional quantum calculations on many-body potential energy surfaces

    Science.gov (United States)

    Bajaj, Pushp; Wang, Xiao-Gang; Carrington, Tucker; Paesani, Francesco

    2018-03-01

    Full-dimensional vibrational spectra are calculated for both X-(H2O) and X-(D2O) dimers (X = F, Cl, Br, I) at the quantum-mechanical level. The calculations are carried out on two sets of recently developed potential energy functions (PEFs), namely, Thole-type model energy (TTM-nrg) and many-body energy (MB-nrg), using the symmetry-adapted Lanczos algorithm with a product basis set including all six vibrational coordinates. Although both TTM-nrg and MB-nrg PEFs are derived from coupled-cluster single double triple-F12 data obtained in the complete basis set limit, they differ in how many-body effects are represented at short range. Specifically, while both models describe long-range interactions through the combination of two-body dispersion and many-body classical electrostatics, the relatively simple Born-Mayer functions employed in the TTM-nrg PEFs to represent short-range interactions are replaced in the MB-nrg PEFs by permutationally invariant polynomials to achieve chemical accuracy. For all dimers, the MB-nrg vibrational spectra are in close agreement with the available experimental data, correctly reproducing anharmonic and nuclear quantum effects. In contrast, the vibrational frequencies calculated with the TTM-nrg PEFs exhibit significant deviations from the experimental values. The comparison between the TTM-nrg and MB-nrg results thus reinforces the notion that an accurate representation of both short-range interactions associated with electron density overlap and long-range many-body electrostatic interactions is necessary for a correct description of hydration phenomena at the molecular level.

  2. FTIR and FT-Raman spectra and density functional computations of the vibrational spectra, molecular geometry and atomic charges of the biomolecule: 5-bromouracil

    Czech Academy of Sciences Publication Activity Database

    Rastogi, V.K.; Palafox, M. A.; Mittal, L.; Peica, N.; Keifer, W.; Lang, Kamil; Ojha, S.P.

    2007-01-01

    Roč. 38, č. 10 (2007), s. 1227-1241 ISSN 0377-0486 Institutional research plan: CEZ:AV0Z40320502 Keywords : FTIR and FT-Raman spectra * density functional computations * molecular geometry Subject RIV: CA - Inorganic Chemistry Impact factor: 3.514, year: 2007

  3. Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

    International Nuclear Information System (INIS)

    Yin Jun; Yu Ling-Yao; Liu Xing; Wan Hui; Lin Zi-Yang; Niu Han-Ben

    2011-01-01

    In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

  4. 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.

  5. Influence of Gamma-Ray Irradiation on Absorption and Fluorescent Spectra of Nd:YAG and Yb:YAG Laser Crystals

    Institute of Scientific and Technical Information of China (English)

    SUN Dun-Lu; ZHANG Qing-Li; XIAO Jing-Zhong; LUO Jian-Qiao; JIANG Hai-He; YIN Shao-Tang

    2008-01-01

    We investigate the influence of gamma-ray irradiation on the absorption and fluorescent spectra of Nd3+ : Y3Al5O12 (Nd:YAG) and Yb3+ :Y3Al5O12 (Yb:YAG) crystals grown by the Czochralski method. Two additional absorption (AA) bands induced by gamma-ray irradiation appear at 255nm and 340nm. The former is eontributed due to Fe3+ impurity, the latter is due to Fe2+ ions and F-type colour centres. The intensity of the excitation and emission spectra as well as the fluorescent lifetime of Nd:YAG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, the same dose irradiation does not impair the fluorescent properties of Yb: YA G crystal. These results indicate that Yb: YA G crystal possesses the advantage over Nd: YA G crystal that has better reliability for applications in harsh radiant environment.

  6. Vibrational spectra and structure of icosahedral anion of monocarba-closo-dodecaborane [CB11H12]- and its nido-derivative: [CB10H13]-

    International Nuclear Information System (INIS)

    Kononova, E.G.; Bukalov, S.S.; Lejtes, L.A.; Lysenko, K.A.; Ol'shevskaya, V.A.

    2003-01-01

    Raman and IR spectra of cesium salts of monocarborane anions [closo-CB 11 H 12 ] - and [nido-CB 10 H 13 ] - were recorded, assignment of frequencies being provided. Quantum-chemical calculation of geometry of the closo-polyhedrons [B 12 H 12 ] 2- and [CB 11 H 12 ] - along with that of frequencies and forms of normal vibrations of the latter was made. Comparison of structural and spectral characteristics in the series of isoelectronic closo-polyhedrons [B 12 H 12 ] 2- , [CB 11 H 12 ] - and p-C 2 B 10 H 12 , as well as those of the closo- and nido structures, was made [ru

  7. COMPARISON OF TWO TEMPERATURE MEASUREMENT METHODS BY UPCONVERSION FLUORESCENCE SPECTRA OF ERBIUM-DOPED LEAD-FLUORIDE NANO-GLASS-CERAMICS

    Directory of Open Access Journals (Sweden)

    V. A. Aseev

    2015-05-01

    Full Text Available The study and compare of two temperature measurement methods is performed for the case of a lead-fluoride nano-glassceramics in the range from 317 to 423 K with a view to their application to temperature sensors. A method of temperature measurement by means of violet, green and red upconversion fluorescence spectra regression on latent structures and a method of temperature measurement by two fluorescence bands intensity ratio in green range are considered. It is shown that a four-dimensional space of latent structures is an optimum one in terms of temperature measurement accuracy. It made possible temperature determining with a relative error not larger than 0.15% at temperatures higher than 340 K by making use of fluorescence spectra training set with the step of 10 K. The method using two green bands fluorescence intensity ratio is inferior by the accuracy. Independence of pump power fluctuations is a significant advantage of the second method. To take advantage of the first method a stabilization of the pump power is necessary. The results of the work can be taken into account while developing optical temperature sensors with a better performance (in relation to accuracy and measurement range compared to existing ones which utilize temperature redistribution of fluorescence intensities in two closely-spaced bands or temperature dependence of fluorescence lifetime.

  8. Fluorescence and excitation spectra of Bk3+, Cf3+, and Es3+ ions in single crystals of LaCl3

    International Nuclear Information System (INIS)

    Hessler, J.P.; Caird, J.A.; Carnall, W.T.; Crosswhite, H.M.; Sjoblom, R.K.; Wagner, F. Jr.

    1978-01-01

    Dye laser techniques have been used to study the energy level structure of the heavier actinides in single crystals of lanthanum chloride. In the case of einsteinium, fluorescence was detected and measured from the following manifolds: J = 5 at 0.984 μm -1 , J = 4 at 1.572 μm -1 , J = 6 at 2.930 μm -1 . This fluorescence was observed to the five lowest manifolds: J = 8, 5, 7, 2, 6. For californium, fluorescence has been detected from the manifolds: J = 11/2 at 1.190 μm -1 , J = 7/2 at 1.389 μm -1 , J = 5/2 at 1.977 μm -1 . This fluorescence was observed to the three lowest manifolds: J = 15/2, 9/2, 11/2. The fluorescence manifolds of berkelium are J = 6 at 1.540 μm -1 , and J = 4 at 1.953 μm -1 . The three lowest manifolds, J = 6, 5, and 4, have been observed in fluorescence. Absorption spectra data have yielded crystal-field splitting measurements in the higher manifolds of Es + . The location of the manifolds in general confirmed earlier approximate free-ion level structure calculations based on assumed regularities in the energy level parameters derived from spectra of the actinide ions through Cf + . 2 figures

  9. DFT calculations of the structures and vibrational spectra of the [Fe(bpy){sub 3}]{sup 2+} and [Ru(bpy){sub 3}]{sup 2+} complexes

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Bruce D. [School of Science, University of Greenwich at Medway, Central Avenue, Chatham Maritime, Kent ME4 4TB (United Kingdom); Dines, Trevor J. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)], E-mail: t.j.dines@dundee.ac.uk; Longhurst, Rayne W. [Division of Electronic Engineering and Physics, University of Dundee, Dundee DD1 4HN (United Kingdom)

    2008-09-03

    Structures of the [M(bpy){sub 3}]{sup 2+} complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy){sub 3}]{sup 2+} which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the {sup 1}E MLCT excited state.

  10. DFT calculations of the structures and vibrational spectra of the [Fe(bpy)3]2+ and [Ru(bpy)3]2+ complexes

    International Nuclear Information System (INIS)

    Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

    2008-01-01

    Structures of the [M(bpy) 3 ] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3 ] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1 E MLCT excited state

  11. DFT calculations of the structures and vibrational spectra of the [Fe(bpy) 3] 2+ and [Ru(bpy) 3] 2+ complexes

    Science.gov (United States)

    Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

    2008-09-01

    Structures of the [M(bpy) 3] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1E MLCT excited state.

  12. Molecular dynamics study of structure and vibrational spectra at zwitterionoic lipid/aqueous KCl, NaCl, and CaCl2 solution interfaces

    Science.gov (United States)

    Ishiyama, Tatsuya; Shirai, Shinnosuke; Okumura, Tomoaki; Morita, Akihiro

    2018-06-01

    Molecular dynamics (MD) simulations of KCl, NaCl, and CaCl2 solution/dipalmytoylphosphatidylcholine lipid interfaces were performed to analyze heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectra in relation to the interfacial water structure. The present MD simulation well reproduces the experimental spectra and elucidates a specific cation effect on the interfacial structure. The K+, Na+, and Ca2+ cation species penetrate in the lipid layer more than the anions in this order, due to the electrostatic interaction with negative polar groups of lipid, and the electric double layer between the cations and anions cancels the intrinsic orientation of water at the water/lipid interface. These mechanisms explain the HD-VSFG spectrum of the water/lipid interface and its spectral perturbation by adding the ions. The lipid monolayer reverses the order of surface preference of the cations at the solution/lipid interface from that at the solution/air interface.

  13. Millimeter-wave and Submillimeter-wave Spectra of Aminoacetonitrile in the Three Lowest Vibrational Excited States

    Energy Technology Data Exchange (ETDEWEB)

    Esposti, Claudio Degli; Dore, Luca; Melosso, Mattia [Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, via Selmi 2, I-40126 Bologna (Italy); Kobayashi, Kaori [Department of Physics, Faculty of Science, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Fujita, Chiho; Ozeki, Hiroyuki, E-mail: ozeki@env.sci.toho-u.ac.jp [Department of Environmental Science, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, 274-8510 (Japan)

    2017-06-01

    It is important to study possible precursors of amino acids such as glycine to enable future searches in interstellar space. Aminoacetonitrile (NH{sub 2}CH{sub 2}CN) is one of the most feasible molecules for this purpose. This molecule was already detected toward Sgr B2(N). Aminoacetonitrile has a few low-lying vibrational excited states, and transitions within these states may be found in space. In this study, the pure-rotational transitions in the three lowest vibrational states in the 80–450 GHz range have been assigned and analyzed. It was found to be very important to include Coriolis coupling between the two lowest vibrational fundamentals, while the third one was unperturbed. The partition function was evaluated considering these new results.

  14. Theoretical investigation of molecular structure and vibrational spectra of 4,5-bis-(2-isopropyl-5- methylphenoxy) phthalonitrile molecule

    International Nuclear Information System (INIS)

    Avci, D.

    2005-01-01

    The molecular geometry and vibrational frequencies of 4,5-bis-(2-isopropyl-5- methylphenoxy) phthalonitrile in the ground state have been calculated using the Hartree- Fock (HF) and density functional method (B3LYP) with 6-31G(d) basis set. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP) show the best agreement with the experimental data. Comparison of the observed fundamental vibrational frequencies of 4,5-bis-(2-isopropyl-5-methylphenoxy) phthalonitrile with calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems

  15. Quantum wavepacket ab initio molecular dynamics: an approach for computing dynamically averaged vibrational spectra including critical nuclear quantum effects.

    Science.gov (United States)

    Sumner, Isaiah; Iyengar, Srinivasan S

    2007-10-18

    We have introduced a computational methodology to study vibrational spectroscopy in clusters inclusive of critical nuclear quantum effects. This approach is based on the recently developed quantum wavepacket ab initio molecular dynamics method that combines quantum wavepacket dynamics with ab initio molecular dynamics. The computational efficiency of the dynamical procedure is drastically improved (by several orders of magnitude) through the utilization of wavelet-based techniques combined with the previously introduced time-dependent deterministic sampling procedure measure to achieve stable, picosecond length, quantum-classical dynamics of electrons and nuclei in clusters. The dynamical information is employed to construct a novel cumulative flux/velocity correlation function, where the wavepacket flux from the quantized particle is combined with classical nuclear velocities to obtain the vibrational density of states. The approach is demonstrated by computing the vibrational density of states of [Cl-H-Cl]-, inclusive of critical quantum nuclear effects, and our results are in good agreement with experiment. A general hierarchical procedure is also provided, based on electronic structure harmonic frequencies, classical ab initio molecular dynamics, computation of nuclear quantum-mechanical eigenstates, and employing quantum wavepacket ab initio dynamics to understand vibrational spectroscopy in hydrogen-bonded clusters that display large degrees of anharmonicities.

  16. Nightglow vibrational distributions in the A3Σu+ and A'3Δu states of O2 derived from astronomical sky spectra

    Directory of Open Access Journals (Sweden)

    T. G. Slanger

    2004-09-01

    Full Text Available Astronomical sky spectra from the Keck I telescope on Mauna Kea have been used to obtain vibrational distributions in the O2A3Σu+ and O2(A'3Δu states from rotationally-resolved Herzberg I and Chamberlain band emissions in the terrestrial nightglow. The A3Σu+ distribution is similar to that presented in earlier publications, with the exception that there is significant population in the previously undiscerned v=0 level. The vibrational distributions of the A'3Δu and A3Σu+ states are essentially the same when comparison is made in terms of the level energies. The intensity of Chamberlain band emission at the peak of the distribution is about one-fourth that of the Herzberg I emission, as previously shown, and may be related primarily to radiative efficiency. The peaks in both population distributions are about 0.25eV below the O(3P+O(3P dissociation limit. We compare these Herzberg state distributions with that of the O2(b1Σg+ state, concurring with others that the intense nightglow emission associated with b1Σg+(v=0 is a reflection of direct transfer from the Herzberg states. This process takes place following O2 collisions, with simultaneous production of very high a1Δg and b1Σg+ vibrational levels.

  17. 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.

  18. Nonlinear generalization of the quasiparticle random phase approximation for description of anharmonic effects in vibrational spectra: Application to the even Ni isotopes

    International Nuclear Information System (INIS)

    Li, C.T.; Klein, A.

    1979-01-01

    The theory of anharmonic nuclear vibrational motion (nonlinear equations-of-motion method) developed in the preceding paper is applied to atsup 60,62,64atNi, which exhibit one and two phonon quadrupole collective states. A model Hamiltonian consisting of a modified pairing plus quadrupole interaction is studied first by comparing the results of the nonlinear equations-of-motion method with those of an exact diagonalization. Contrary to popular opinion, the model chosen fails to produce a vibrational spectrum, except in the case of 60 Ni, and as a consequence, the nonlinear equations-of-motion method, designed specifically to describe vibrational spectra, accords well with the exact calculations only for this case. A simple method is then described, within the framework of the nonlinear equations-of-motion method, for refining the model Hamiltonian so as to bring it into accord with experiment. In practice, it is found that a simple additional parameter in the Hamiltonian suffices to yield descriptions of the quadrupole states in Ni isotopes comparable in precision to the most up-to-date versions (modified, adjusted, etc.) of the surface delta interaction model

  19. Vibrational Spectra of β″-Type BEDT-TTF Salts: Relationship between Conducting Property, Time-Averaged Site Charge and Inter-Molecular Distance

    Directory of Open Access Journals (Sweden)

    Takashi Yamamoto

    2012-07-01

    Full Text Available The relationship between the conducting behavior and the degree of charge fluctuation in the β″-type BEDT-TTF salts is reviewed from the standpoints of vibrational spectroscopy and crystal structure. A group of β″-type ET salts demonstrates the best model compounds for achieving the above relationship because the two-dimensional structure is simple and great diversity in conducting behavior is realized under ambient pressure. After describing the requirement for the model compound, the methodology for analyzing the results of the vibrational spectra is presented. Vibrational spectroscopy provides the time-averaged molecular charge, the charge distribution in the two-dimensional layer, and the inter-molecular interactions, etc. The experimental results applied to 2/3-filled and 3/4-filled β″-type ET salts are reported. These experimental results suggest that the conducting property, the difference in the time-averaged molecular charges between the ionic and neutral-like sites, the alternation in the inter-molecular distances and the energy levels in the charge distributions are relevant to one another. The difference in the time-averaged molecular charges, ∆ρ, is a useful criterion for indicating conducting behavior. All superconductors presented in this review are characterized as small but finite ∆ρ.

  20. A complete assignment of the vibrational spectra of 2-furoic acid based on the structures of the more stable monomer and dimer

    Science.gov (United States)

    Ghalla, Houcine; Issaoui, Noureddine; Castillo, María Victoria; Brandán, Silvia Antonia; Flakus, Henryk T.

    2014-03-01

    The structural and vibrational properties of cyclic dimer of 2-furoic acid (2FA) were predicted by combining the available experimental infrared and Raman spectra in the solid phase and ab initio calculations based on density functional theory (DFT) with Pople's basis sets. The calculations show that there are two cyclic dimers for the title molecule that have been theoretically determined in the gas phase, and that only one of them, cis conformer, is present in the solid phase. The complete assignment of the 66 normal vibrational modes for the cis cyclic dimer was performed using the Pulay's Scaled Quantum Mechanics Force Field (SQMFF) methodology. Four strong bands in the infrared spectrum at 1583, 1427, 1126 and 887 cm-1 and the group of bands in the Raman spectrum at 1464, 1452, 1147, 1030, 885, 873, 848, 715 and 590 cm-1 are characteristic of the dimeric form of 2FA in the solid phase. In this work, the calculated structural and vibrational properties of both dimeric species were analyzed and compared between them. In addition, three types of atomic charges, bond orders, possible charge transfer, topological properties of the furan rings, Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) theory calculations were employed to study the stabilities and intermolecular interactions of the both dimers of 2FA.

  1. A QUANTUM BAND MODEL OF THE ν3 FUNDAMENTAL OF METHANOL (CH3OH) AND ITS APPLICATION TO FLUORESCENCE SPECTRA OF COMETS

    International Nuclear Information System (INIS)

    Villanueva, G. L.; DiSanti, M. A.; Mumma, M. J.; Xu, L.-H.

    2012-01-01

    Methanol (CH 3 OH) radiates efficiently at infrared wavelengths, dominating the C-H stretching region in comets, yet inadequate quantum-mechanical models have imposed limits on the practical use of its emission spectra. Accordingly, we constructed a new line-by-line model for the ν 3 fundamental band of methanol at 2844 cm –1 (3.52 μm) and applied it to interpret cometary fluorescence spectra. The new model permits accurate synthesis of line-by-line spectra for a wide range of rotational temperatures, ranging from 10 K to more than 400 K. We validated the model by comparing simulations of CH 3 OH fluorescent emission with measured spectra of three comets (C/2001 A2 LINEAR, C/2004 Q2 Machholz and 8P/Tuttle) acquired with high-resolution infrared spectrometers at high-altitude sites. The new model accurately describes the complex emission spectrum of the ν 3 band, providing distinct rotational temperatures and production rates at greatly improved confidence levels compared with results derived from earlier fluorescence models. The new model reconciles production rates measured at infrared and radio wavelengths in C/2001 A2 (LINEAR). Methanol can now be quantified with unprecedented precision and accuracy in astrophysical sources through high-dispersion spectroscopy at infrared wavelengths.

  2. [Study on crystal growth and vibrational spectra of Yb(x) : KY(1-x) (WO4)2].

    Science.gov (United States)

    Liu, Jing-He; Zhang, Ying; Zhang, Li-Jie; Zeng, Fan-Ming; Wang, Cheng-Wei; Zhang, Xue-Jian

    2008-02-01

    Yb(x) : KY(1-x)W (x = 0.05)and KYbW crystals were grown by TSSG method. Both of the structure and spectral properties were compared. The condition for the crystal growth is: the rotation rate 10-15 r x min(-1), the pulling speed 1-2 d(-1), the growing period 10-15 d, cooling growing speed 0.05-0.1 degrees C x h(-1), and the cooling speed 20 degrees C x h(-1). X-ray powder diffraction analysis was performed for the crystal powder. They belong to beta-KYW structure with low thermal phase. The cell parameters of the two crystals were calculated, and they are respectively a1 = 1.063 nm, b1 = 1.034 nm, c1 = 0.755 nm, beta1 = 130.75 degrees, Z1 = 4 and a2 = 1.061 nm, b2 = 1.029 nm, c2 = 0.749 nm, beta2 = 130.65 degrees and Z2 = 4. The infrared spectrum and Raman spectrum of crystal were measured. The sample of Yb(x) : KY(1-x) W (x = 0.05) had stronger infrared absorption peaks at 925, 891, 840, 777 and 749 cm(-1), which were caused by stretching vibration. The sample of KYW had stronger infrared absorption peaks at 484 and 437 cm(-1) caused by bending vibration. The vibration modes were analysed and vibrational frequencies of vibratory activity was assigned. The two crystals had strong Raman activity. The vibration of WOOW and WOW exists from 200 to 1000 cm(-1).

  3. Regio-Regular Oligo and Poly(3-hexyl thiophene): Precise Structural Markers from the Vibrational Spectra of Oligomer Single Crystals.

    KAUST Repository

    Brambilla, Luigi; Tommasini, Matteo; Botiz, Ioan; Rahimi, Khosrow; Agumba, John O.; Stingelin, Natalie; Zerbi, Giuseppe

    2014-01-01

    , namely, amorphous, semicrystalline, polycrystalline and single crystal. We have based our analysis on the spectra of the (3HT)8 single crystal (whose structure has been determined by selected area electron diffraction) taken as reference

  4. Structure and vibrational spectra of melaminium bis(trifluoroacetate) trihydrate: FT-IR, FT-Raman and quantum chemical calculations

    Science.gov (United States)

    Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Marchewka, M. K.; Gunasekaran, S.; Anbalagan, G.

    Melaminium bis(trifluoroacetate) trihydrate (MTFA), an organic material has been synthesized and single crystals of MTFA have been grown by the slow solvent evaporation method at room temperature. X-ray powder diffraction analysis confirms that MTFA crystal belongs to the monoclinic system with space group P2/c. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional theory (DFT) B3LYP method with 6-311G(d,p) and 6-311++G(d,p) basis sets. The X-ray diffraction data have been compared with the data of optimized molecular structure. The theoretical results show that the crystal structure can be reproduced by optimized geometry and the vibrational frequencies show good agreement with the experimental values. The nuclear magnetic resonance (NMR) chemical shift of the molecule has been calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. HOMO-LUMO, and other related molecular and electronic properties are calculated. The Mulliken and NBO charges have also been calculated and interpreted.

  5. IUPAC critical evaluation of the rotational–vibrational spectra of water vapor, Part III: Energy levels and transition wavenumbers for H216O

    International Nuclear Information System (INIS)

    Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Császár, Attila G.; Daumont, Ludovic; Gamache, Robert R.; Hodges, Joseph T.; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Vandaele, Ann Carine; Zobov, Nikolai F.; Al Derzi, Afaf R.; Fábri, Csaba; Fazliev, Alexander Z.; Furtenbacher, Tibor

    2013-01-01

    This is the third of a series of articles reporting critically evaluated rotational–vibrational line positions, transition intensities, and energy levels, with associated critically reviewed labels and uncertainties, for all the main isotopologues of water. This paper presents experimental line positions, experimental-quality energy levels, and validated labels for rotational–vibrational transitions of the most abundant isotopologue of water, H 2 16 O. The latest version of the MARVEL (Measured Active Rotational–Vibrational Energy Levels) line-inversion procedure is used to determine the rovibrational energy levels of the electronic ground state of H 2 16 O from experimentally measured lines, together with their self-consistent uncertainties, for the spectral region up to the first dissociation limit. The spectroscopic network of H 2 16 O containstwo components, an ortho (o) and a para (p) one. For o-H 2 16 O and p-H 2 16 O, experimentally measured, assigned, and labeled transitions were analyzed from more than 100 sources. The measured lines come from one-photon spectra recorded at room temperature in absorption, from hot samples with temperatures up to 3000 K recorded in emission, and from multiresonance excitation spectra which sample levels up to dissociation. The total number of transitions considered is 184 667 of which 182 156 are validated: 68 027 between para states and 114 129 ortho ones. These transitions give rise to 18 486 validated energy levels, of which 10 446 and 8040 belong to o-H 2 16 O and p-H 2 16 O, respectively. The energy levels, including their labeling with approximate normal-mode and rigid-rotor quantum numbers, have been checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators as well as against previous compilations of energy levels. The extensive list of MARVEL lines and levels obtained are deposited in the supplementary data of this paper, as well as in a

  6. State-of-the art comparability of corrected emission spectra. 2. Field laboratory assessment of calibration performance using spectral fluorescence standards.

    Science.gov (United States)

    Resch-Genger, Ute; Bremser, Wolfram; Pfeifer, Dietmar; Spieles, Monika; Hoffmann, Angelika; DeRose, Paul C; Zwinkels, Joanne C; Gauthier, François; Ebert, Bernd; Taubert, R Dieter; Voigt, Jan; Hollandt, Jörg; Macdonald, Rainer

    2012-05-01

    In the second part of this two-part series on the state-of-the-art comparability of corrected emission spectra, we have extended this assessment to the broader community of fluorescence spectroscopists by involving 12 field laboratories that were randomly selected on the basis of their fluorescence measuring equipment. These laboratories performed a reference material (RM)-based fluorometer calibration with commercially available spectral fluorescence standards following a standard operating procedure that involved routine measurement conditions and the data evaluation software LINKCORR developed and provided by the Federal Institute for Materials Research and Testing (BAM). This instrument-specific emission correction curve was subsequently used for the determination of the corrected emission spectra of three test dyes, X, QS, and Y, revealing an average accuracy of 6.8% for the corrected emission spectra. This compares well with the relative standard uncertainties of 4.2% for physical standard-based spectral corrections demonstrated in the first part of this study (previous paper in this issue) involving an international group of four expert laboratories. The excellent comparability of the measurements of the field laboratories also demonstrates the effectiveness of RM-based correction procedures.

  7. 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

  8. Effect of anthocyanins, carotenoids, and flavonols on chlorophyll fluorescence excitation spectra in apple fruit: signature analysis, assessment, modelling, and relevance to photoprotection.

    Science.gov (United States)

    Merzlyak, Mark N; Melø, Thor Bernt; Naqvi, K Razi

    2008-01-01

    Whole apple fruit (Malus domestica Borkh.) widely differing in pigment content and composition has been examined by recording its chlorophyll fluorescence excitation and diffuse reflection spectra in the visible and near UV regions. Spectral bands sensitive to the pigment concentration have been identified, and linear models for non-destructive assessment of anthocyanins, carotenoids, and flavonols via chlorophyll fluorescence measurements are put forward. The adaptation of apple fruit to high light stress involves accumulation of these protective pigments, which absorb solar radiation in broad spectral ranges extending from UV to the green and, in anthocyanin-containing cultivars, to the red regions of the spectrum. In ripening apples the protective effect in the blue region could be attributed to extrathylakoid carotenoids. A simple model, which allows the simulation of chlorophyll fluorescence excitation spectra in the visible range and a quantitative evaluation of competitive absorption by anthocyanins, carotenoids, and flavonols, is described. Evidence is presented to support the view that anthocyanins, carotenoids, and flavonols play, in fruit with low-to-moderate pigment content, the role of internal traps (insofar as they compete with chlorophylls for the absorption of incident light in specific spectral bands), affecting thereby the shape of the chlorophyll fluorescence excitation spectrum.

  9. L-lysine-L-tartaric acid: New molecular complex with nonlinear optical properties. Structure, vibrational spectra and phase transitions

    International Nuclear Information System (INIS)

    Debrus, S.; Marchewka, M.K.; Baran, J.; Drozd, M.; Czopnik, R.; Pietraszko, A.; Ratajczak, H.

    2005-01-01

    The first X-ray diffraction and vibrational spectroscopic analysis of a novel complex between L-lysine and L-tartaric acid is reported. The structure was solved in two temperatures (320 and 260 K) showing incommensurate phase between them. Room-temperature powder infrared and Raman measurements for the L-lysine-L-tartaric acid molecular complex (1:1) were carried out. DSC measurements on powder samples indicate two phase transitions points at about 295, 300 and 293, 300 K, for heating and cooling, respectively, with noticeable temperature interval between them. Second harmonic generation efficiency d eff =0.35 d eff (KDP)

  10. Simultaneous analysis of rotational and vibrational-rotational spectra of DF and HF to obtain irreducible molecular constants for HF

    International Nuclear Information System (INIS)

    Horiai, Koui; Uehara, Hiromichi

    2011-01-01

    Graphical abstract: Available rotational and vibrational-rotational spectral lines of DF and HF are analyzed simultaneously using a non-Born-Oppenheimer effective Hamiltonian. Research highlights: → Simultaneous analysis of DF and HF spectral data. → Application of a non-Born-Oppenheimer effective Hamiltonian. → Twenty irreducible molecular constants for HF have been determined. - Abstract: Analytic expressions of corrections for the breakdown of the Born-Oppenheimer approximation to Dunham's Y ij with optimal parameters, i.e., determinable clusters of expansion coefficients, are applied to a data analysis of the rotational and vibrational-rotational transitions of HF reported in the literature. All the available spectral lines of the two isotopologues, DF and HF, are simultaneously fitted to a single set of molecular parameters of HF within experimental errors. Fitting of a data set of 595 spectral transitions for DF and HF has generated only 20 minimal independent parameter values, i.e., 'irreducible' molecular constants of HF, that are sufficient to precisely generate 82 Y ij coefficients and 144 band constants in total: 41 Y ij and 72 band constants each for DF and HF.

  11. Adaptive vibrational configuration interaction (A-VCI): A posteriori error estimation to efficiently compute anharmonic IR spectra

    Science.gov (United States)

    Garnier, Romain; Odunlami, Marc; Le Bris, Vincent; Bégué, Didier; Baraille, Isabelle; Coulaud, Olivier

    2016-05-01

    A new variational algorithm called adaptive vibrational configuration interaction (A-VCI) intended for the resolution of the vibrational Schrödinger equation was developed. The main advantage of this approach is to efficiently reduce the dimension of the active space generated into the configuration interaction (CI) process. Here, we assume that the Hamiltonian writes as a sum of products of operators. This adaptive algorithm was developed with the use of three correlated conditions, i.e., a suitable starting space, a criterion for convergence, and a procedure to expand the approximate space. The velocity of the algorithm was increased with the use of a posteriori error estimator (residue) to select the most relevant direction to increase the space. Two examples have been selected for benchmark. In the case of H2CO, we mainly study the performance of A-VCI algorithm: comparison with the variation-perturbation method, choice of the initial space, and residual contributions. For CH3CN, we compare the A-VCI results with a computed reference spectrum using the same potential energy surface and for an active space reduced by about 90%.

  12. Vibrational spectra, molecular structure, NBO, HOMO-LUMO and first order hyperpoalarizability analysis of 1,4-bis(4-formylphenyl)anthraquinone by density functional theory

    Science.gov (United States)

    Renjith, R.; Mary, Y. Sheena; Varghese, Hema Tresa; Panicker, C. Yohannan; Thiemann, Thies; Van Alsenoy, Christian

    2014-10-01

    Anthraquinone derivatives are most important class of a system that absorb in the visible region. Infrared and Raman spectroscopic analyses were carried out on 1,4-bis(4-formylphenyl)anthraquinone. The interpretation of the spectra was aided by DFT calculations of the molecule. The vibrational wavenumbers were examined theoretically using the Gaussian09 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. A computation of the first hyperpolarizability of the compound indicates that this class of substituted anthraquinones may be a good candidate as a NLO material. Optimized geometrical parameters of the compound are in agreement with similar reported structures. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis.

  13. Calculations of the electronic levels, spin-Hamiltonian parameters and vibrational spectra for the CrCl{sub 3} layered crystals

    Energy Technology Data Exchange (ETDEWEB)

    Avram, C.N. [Faculty of Physics, West University of Timisoara, Bd. V. Parvan No. 4, 300223 Timisoara (Romania); Gruia, A.S., E-mail: adigruia@yahoo.com [Faculty of Physics, West University of Timisoara, Bd. V. Parvan No. 4, 300223 Timisoara (Romania); Brik, M.G. [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Institute of Physics, University of Tartu, Ravila 14C, Tartu 50411 (Estonia); Institute of Physics, Jan Dlugosz University, Armii Krajowej 13/15, PL-42200 Czestochowa (Poland); Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland); Barb, A.M. [Faculty of Physics, West University of Timisoara, Bd. V. Parvan No. 4, 300223 Timisoara (Romania)

    2015-12-01

    Calculations of the Cr{sup 3+} energy levels, spin-Hamiltonian parameters and vibrational spectra for the layered CrCl{sub 3} crystals are reported for the first time. The crystal field parameters and the energy level scheme were calculated in the framework of the Exchange Charge Model of crystal field. The spin-Hamiltonian parameters (zero-field splitting parameter D and g-factors) for Cr{sup 3+} ion in CrCl{sub 3} crystals were obtained using two independent techniques: i) semi-empirical crystal field theory and ii) density functional theory (DFT)-based model. In the first approach, the spin-Hamiltonian parameters were calculated from the perturbation theory method and the complete diagonalization (of energy matrix) method. The infrared (IR) and Raman frequencies were calculated for both experimental and fully optimized geometry of the crystal structure, using CRYSTAL09 software. The obtained results are discussed and compared with the experimental available data.

  14. The molecular structure and vibrational spectra of N-(2,2-diphenylacetyl)- N'-(naphthalen-1yl)-thiourea by Hartree-Fock and density functional methods

    Science.gov (United States)

    Arslan, Hakan; Mansuroglu, Demet Sezgin; VanDerveer, Don; Binzet, Gun

    2009-04-01

    N-(2,2-Diphenylacetyl)- N'-(naphthalen-1yl)-thiourea (PANT) has been synthesized and characterized by elemental analysis, IR spectroscopy and 1H NMR spectroscopy. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1, Z = 2 with a = 10.284(2) Å, b = 10.790(2) Å, c = 11.305(2) Å, α = 64.92(3)°, β = 89.88(3)°, γ = 62.99(3)°, V = 983.7(3) Å 3 and Dcalc = 1.339 Mg/m 3. The molecular structure, vibrational frequencies and infrared intensities of PANT were calculated by the Hartree-Fock and density functional theory methods (BLYP and B3LYP) using the 6-31G* basis set. The calculated geometric parameters were compared to the corresponding X-ray structure of the title compound. We obtained 22 stable conformers for the title compound; however Conformer 1 is approximately 9.53 kcal/mol more stable than Conformer 22. The comparison of the theoretical and experimental geometry of the title compound shows that the X-ray parameters fairly well reproduce the geometry of Conformer 17. The harmonic vibrations computed for this compound by the B3LYP/6-31G* method are in good agreement with the observed IR spectral data. Theoretical vibrational spectra of the title compound were interpreted by means of PEDs using the VEDA 4 program. A general better performance of the investigated methods was calculated by PAVF 1.0 program.

  15. Vibrational spectra, molecular structure, natural bond orbital, first order hyperpolarizability, thermodynamic analysis and normal coordinate analysis of Salicylaldehyde p-methylphenylthiosemicarbazone by density functional method

    Science.gov (United States)

    Porchelvi, E. Elamurugu; Muthu, S.

    2015-01-01

    The thiosemicarbazone compound, Salicylaldehyde p-methylphenylthiosemicarbazone (abbreviated as SMPTSC) was synthesized and characterized by FTIR, FT-Raman and UV. Density functional (DFT) calculations have been carried out for the title compound by performing DFT level of theory using B3LYP/6-31++G(d,p) basis set. The molecular geometry and vibrational frequencies were calculated and compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using density functional theory (DFT/B3LYP) with 6-311++G(d,p) basis set. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. Thearomaticities of the phenyl rings were studied using the standard harmonic oscillator model of aromaticity (HOMA) index. Mulliken population analysis on atomic charges is also calculated. The molecule orbital contributions are studied by density of energy states (DOSs).

  16. Ab initio molecular orbital studies of the vibrational spectra of the van der Waals complexes of boron trifluoride with the noble gases.

    Science.gov (United States)

    Ford, Thomas A

    2005-05-01

    The molecular structures, interaction energies, charge transfer properties and vibrational spectra of the van der Waals complexes formed between boron trifluoride and the noble gases neon, argon, krypton and xenon have been computed using second and fourth order Møller-Plesset perturbation theory and the Los Alamos National Laboratory LANL2DZ basis set. The complexes are all symmetric tops, with the noble gas atom acting as a sigma electron donor along the C3 axis of the BF3 molecule. The interaction energies are all vanishingly small, and the amount of charge transferred in each case is of the order of 0.01e. The directions of the wavenumber shifts of the symmetric bending (nu2) and antisymmetric stretching (nu3) modes of the BF3 fragment confirm those determined experimentally, and the shifts are shown to correlate well with the polarizability of the noble gas atom and the inverse sixth power of the intermonomer separation. The nu2 mode is substantially more sensitive to complexation than the nu3 vibration.

  17. Improved assignments of the vibrational fundamental modes of ortho -, meta -, and para -xylene using gas- and liquid-phase infrared and Raman spectra combined with ab initio calculations: Quantitative gas-phase infrared spectra for detection

    Energy Technology Data Exchange (ETDEWEB)

    Lindenmaier, Rodica; Scharko, Nicole K.; Tonkyn, Russell G.; Nguyen, Kiet T.; Williams, Stephen D.; Johnson, Timothy J.

    2017-07-25

    Xylenes contain a blend of the ortho-, meta-, and para- isomers, and all are abundant contaminants in the ground, surface waters, and air. To better characterize xylene and to better enable its detection, we report high quality quantitative vapor-phase infrared spectra of all three isomers over the 540-6500 cm-1 range. All fundamental vibrational modes are assigned based on these vapor-phase infrared spectra, liquid-phase infrared and Raman spectra, along with density functional theory (DFT), ab initio MP2 and high energy-accuracy compound theoretical model (W1BD) calculations. Both MP2 and DFT predict a single conformer with C2v symmetry for ortho-xylene, and two conformers each for meta- and para-xylene, depending on the preferred orientations of the methyl groups. For meta-xylene the two conformers have Cs and C2 symmetry, and for para-xylene these conformers have C2v or C2h symmetry. Since the relative population of the two conformers is approximately 50% for both isomers and predicted frequencies and intensities are very similar for each conformer, we made an arbitrary choice to discuss the Cs conformer for meta-xylene and the C2v conformer for para-xylene. We report integrated band intensities for all isomers. Using the quantitative infrared data, we determine the global warming potential values of each isomer and discuss potential bands for atmospheric monitoring.

  18. Vibrational Spectra And Potential Energy Distributions of Normal Modes of N,N'-Etilenbis(P-Toluen sulfonamide)

    International Nuclear Information System (INIS)

    Alyar, S.

    2008-01-01

    N-substituted sulfonamides are well known for their diuretic, antidiabetic, antibacterial and antifungal, anticancer e.g., and are widely used in the therapy of patients. These important bioactive properties are strongly affected by the special features of -CH 2 -SO 2 -NR-linker and intramolecular motion Thus, the studies of energetic and spatial properties on N-substituted sulfonamides are of great importance to improve our understanding of their biological activities and enhance abilities to predict new drugs. Density Functional Theory B3LYP /6-31G(d,p) level has been applied to obtain the vibrational force field for the most stable conformation of N,N'-etilenbis(p-toluensulfonamit)(ptsen)having sulfonamide moiety. The results of these calculation have been compared with spectroscopic data to verify accuracy of calculation and applicability of the DFT approach to ptsen. Additionally, complete normal coordinate analyses with quantum mechanical scaling (SQM) were performed to derive the potential energy distributions (PE)

  19. Intra- versus Intermolecular Hydrogen Bonding: Solvent-Dependent Conformational Preferences of a Common Supramolecular Binding Motif from 1 H NMR and Vibrational Circular Dichroism Spectra.

    Science.gov (United States)

    Demarque, Daniel P; Merten, Christian

    2017-12-19

    When predicting binding properties of small molecules or larger supramolecular aggregates, intra- and intermolecular hydrogen bonds are often considered the most important factor. Spectroscopic techniques such as 1 H NMR spectroscopy are typically utilized to characterize such binding events, but interpretation is often qualitative and follows chemical intuition. In this study, we compare the effects of intramolecular hydrogen bonding and solvation on two chiral 2,6-pyridinediyl-dialkylamides. In comparison with 1 H NMR spectroscopy, vibrational circular dichroism (VCD) spectroscopy proved to be more sensitive to conformational changes. In fact, the change of the solvent from CDCl 3 to [D 6 ]DMSO generates mirror-image VCD spectra for the same enantiomer. Here, the common sense that the sterically less hindered group is more prone to solvation proved to be wrong according predicted VCD spectra, which clearly show that both asymmetric amide hydrogens are equally likely to be solvated, but never simultaneously. The competition between intra- and intermolecular hydrogen bonding and their importance for a correct prediction of spectral properties are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and thieno[3,2-c]coumarins derivatives: structure, electronic spectra and TD-DFT study

    Science.gov (United States)

    Akchurin, Igor O.; Yakhutina, Anna I.; Bochkov, Andrei Y.; Solovjova, Natalya P.; Medvedev, Michael G.; Traven, Valerii F.

    2018-05-01

    Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and 7-(diethylamino)thieno[3,2-c]coumarins derivatives have been synthesized using formyl derivatives of furo- and thieno[3,2-c]coumarins as starting materials. Electron absorption and fluorescent spectra of the dyes have been recorded in different solvents. Structure and solvent effects on the dyes spectral characteristics were analyzed. The fusion of five-membered heterocycle to coumarin provides a definite increase of Stokes shifts in all solvents and results in higher quantum yields of fluorescence. The absorption and emission bands of thieno[3,2-c] coumarin derivatives are definitely shifted to the red region (3-30 nm) compared to similar derivatives of furo[3,2-c]coumarin. TD-DFT calculations of some of the studied compounds have shown that hybrid DFT functionals and adequate representation of molecular environment are essential for obtaining accurate UV-Vis absorption spectra for the dyes with extended π-system. The longest-wave electron transitions in the studied compounds were computationally shown to be of push-pull nature.

  1. FT-IR, FT-Raman, NMR spectra, density functional computations of the vibrational assignments (for monomer and dimer) and molecular geometry of anticancer drug 7-amino-2-methylchromone

    Science.gov (United States)

    Mariappan, G.; Sundaraganesan, N.

    2014-04-01

    Vibrational assignments for the 7-amino-2-methylchromone (abbreviated as 7A2MC) molecule using a combination of experimental vibrational spectroscopic measurements and ab initio computational methods are reported. The optimized geometry, intermolecular hydrogen bonding, first order hyperpolarizability and harmonic vibrational wavenumbers of 7A2MC have been investigated with the help of B3LYP density functional theory method. The calculated molecular geometry parameters, the theoretically computed vibrational frequencies for monomer and dimer and relative peak intensities were compared with experimental data. DFT calculations using the B3LYP method and 6-31 + G(d,p) basis set were found to yield results that are very comparable to experimental IR and Raman spectra. Detailed vibrational assignments were performed with DFT calculations and the potential energy distribution (PED) obtained from the Vibrational Energy Distribution Analysis (VEDA) program. Natural Bond Orbital (NBO) study revealed the characteristics of the electronic delocalization of the molecular structure. 13C and 1H NMR spectra have been recorded and 13C and 1H nuclear magnetic resonance chemical shifts of the molecule have been calculated using the gauge independent atomic orbital (GIAO) method. Furthermore, All the possible calculated values are analyzed using correlation coefficients linear fitting equation and are shown strong correlation with the experimental data.

  2. Crystal and molecular structure of N-(4-nitrophenyl)-β-alanine—Its vibrational spectra and theoretical calculations

    Science.gov (United States)

    Marchewka, M. K.; Drozd, M.; Janczak, J.

    2011-08-01

    The N-(4-nitrophenyl)-β-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title β-alanine derivative crystallizes in the P2 1/ c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of β-alanine derivative molecule has been compared with those obtained by molecular orbital calculations corresponding to the gas phase. In the crystal the molecules related by an inversion center interact via symmetrically equivalent O-H⋯O hydrogen bonds with O⋯O distance of 2.656(2) Å forming a dimeric structure. The dimers of β-alanine derivative weakly interact via N-H⋯O hydrogen bonds between the H atom of β-amine groups and one of O atom of nitro groups. The room temperature powder vibrational (infrared and Raman) measurements are in accordance with the X-ray analysis. In aqueous solution of 4-nitroaniline and acrylic acid, the double C dbnd C bond of vinyl group of acrylic acid breaks as result of 4-nitroaniline addition.

  3. Theoretical Study on Vibrational Spectra, Detonation Properties and Pyrolysis Mechanism for Cyclic 2-Diazo-4,6-dinitrophenol

    Science.gov (United States)

    Li, Xiao-hong; Yin, Geng-xin; Zhang, Xian-zhou

    2012-10-01

    Based on the full optimized molecular geometrical structures at the DFT-B3LYP/6-311+G** level, there exists intramolecular hydrogen bond interaction for cyclic 2-diazo-4,6-dinitrophenol. The assigned infrared spectrum is obtained and used to compute the thermodynamic properties. The results show that there are four main characteristic regions in the calculated IR spectra of the title compound. The detonation velocities and pressures are also evaluated by using Kamlet-Jacobs equations based on the calculated density and condensed phase heat of formation. Thermal stability and the pyrolysis mechanism of 2-diazo-4,6-dinitrophenol are investigated by calculating the bond dissociation energies at the B3LYP/6-311+G** level.

  4. Vibrational spectra and assignments for cis- and trans-1,2-difluorocyclopropane and three deuterium substituted modifications of each isomer

    International Nuclear Information System (INIS)

    Craig, N.C.; Hu Chao, T.N.; Cuellar, E.; Hendriksen, D.E.; Koepke, J.W.

    1975-01-01

    Infrared spectra under a variety of experimental conditions and Raman spectra for the liquid phase have been recorded for the cis and trans isomers of 1,2-difluorocyclopropane and the 1,2-d 2 , 3,3-d 2 , and d 4 deuterated modifications. Almost all of the 168 fundamentals of this set of eight molecules have been observed and assigned convincingly. For cis-1,2-difluorocyclopropane-d 0 the fundamentals are (a') 3105, 3063, 3023, 1450, 1365, 1224, 1135, 1047, 862, 784, 468, 209 cm -1 ; (a'') 3055, 1346, 1150, 1089, 1060, 993, 739, 621, 319 cm -1 . For trans-1,2-difluorocyclopropane-d 0 the fundamentals are (a) 3070, 3021, 1457, 1380, 1203, 1132, 1068, 961, 842, 415, 279 cm -1 ; (b) 3110, 3070, 1304, 1161, 1072, 1005, 937, 783, 452, 303 cm -1 . Only the 1089-cm -1 mode in the cis and the 937-cm -1 mode in the trans are in doubt. Group frequency descriptions are discussed qualitatively, and attention is drawn to the fundamentals near 1450 cm -1 which are characteristic of fluorocyclopropanes and appear to be largely due to ring stretching. From previously published equilibrium data for the cis-to-trans isomerization and the fundamental frequencies of the two isomers, an electronic energy difference of -2800 +- 200 cal/mol has been calculated. In contrast, the trans isomer of 1,2-difluoroethylene has an energy 1100 cal/mol greater than the cis, and the trans rotamer of 1,2-difluoroethane has an energy about 600 cal/mol greater than the gauche. (auth)

  5. Communication: On the consistency of approximate quantum dynamics simulation methods for vibrational spectra in the condensed phase.

    Science.gov (United States)

    Rossi, Mariana; Liu, Hanchao; Paesani, Francesco; Bowman, Joel; Ceriotti, Michele

    2014-11-14

    Including quantum mechanical effects on the dynamics of nuclei in the condensed phase is challenging, because the complexity of exact methods grows exponentially with the number of quantum degrees of freedom. Efforts to circumvent these limitations can be traced down to two approaches: methods that treat a small subset of the degrees of freedom with rigorous quantum mechanics, considering the rest of the system as a static or classical environment, and methods that treat the whole system quantum mechanically, but using approximate dynamics. Here, we perform a systematic comparison between these two philosophies for the description of quantum effects in vibrational spectroscopy, taking the Embedded Local Monomer model and a mixed quantum-classical model as representatives of the first family of methods, and centroid molecular dynamics and thermostatted ring polymer molecular dynamics as examples of the latter. We use as benchmarks D2O doped with HOD and pure H2O at three distinct thermodynamic state points (ice Ih at 150 K, and the liquid at 300 K and 600 K), modeled with the simple q-TIP4P/F potential energy and dipole moment surfaces. With few exceptions the different techniques yield IR absorption frequencies that are consistent with one another within a few tens of cm(-1). Comparison with classical molecular dynamics demonstrates the importance of nuclear quantum effects up to the highest temperature, and a detailed discussion of the discrepancies between the various methods let us draw some (circumstantial) conclusions about the impact of the very different approximations that underlie them. Such cross validation between radically different approaches could indicate a way forward to further improve the state of the art in simulations of condensed-phase quantum dynamics.

  6. A theoretical study of the molecular structures and vibrational spectra of the N 2O⋯(HF) 2

    Science.gov (United States)

    de Lima, Nathália B.; Ramos, Mozart N.

    2012-01-01

    Theoretical calculations using both the MP2 and B3LYP levels of calculation with a 6-311++G(3df,3pd) basis set have been performed to determine stable structures and molecular properties for the H-bonded complexes involving nitrous oxide (N 2O) and two HF molecules. Five complex have been characterized as minima since no imaginary frequency was found. Three complex are predicted to be relatively more stable with binding energies varying from 14 kJ mol -1 to 23 kJ mol -1 after BSSE and ZPE corrections. Our calculations have revealed that the second complexation with HF preferably occurs with the first complexed HF molecule, i.e., forming the X⋯H sbnd F⋯H sbnd F skeleton with X = O or N instead the F sbnd H⋯N sbnd N sbnd O⋯H sbnd F one. As expected, the H sbnd F chemical bonds are increased after complexation due to intermolecular charge transfer from "n" isolated pair of the X atom (X = N, O or F) to the σ ∗ anti-bonding orbital of HF. For the strongly bounded complex, the doubly complexed HF molecule acts as a bridge between the two end molecules while transferring electrons from N 2O to HF. Both possess the same amount of residual charge but with opposite signs. The H sbnd F stretching frequency of the monoprotic acid is shifted downward after complexation whereas its IR intensity is much enhanced. This increase has been adequately interpreted in terms of equilibrium hydrogen charge and charge-flux associated to the H sbnd F stretching using the CCFOM model for infrared intensities. This procedure has also allowed to analyze the new vibrational modes arising upon H-bond formation, especially those associated with the out-of-plane and in-plane HF bending modes, which are pure rotations in the HF isolated molecule.

  7. Direct observation of vibrational energy dispersal via methyl torsions.

    Science.gov (United States)

    Gardner, Adrian M; Tuttle, William D; Whalley, Laura E; Wright, Timothy G

    2018-02-28

    Explicit evidence for the role of methyl rotor levels in promoting energy dispersal is reported. A set of coupled zero-order vibration/vibration-torsion (vibtor) levels in the S 1 state of para -fluorotoluene ( p FT) are investigated. Two-dimensional laser-induced fluorescence (2D-LIF) and two-dimensional zero-kinetic-energy (2D-ZEKE) spectra are reported, and the assignment of the main features in both sets of spectra reveals that the methyl torsion is instrumental in providing a route for coupling between vibrational levels of different symmetry classes. We find that there is very localized, and selective, dissipation of energy via doorway states, and that, in addition to an increase in the density of states, a critical role of the methyl group is a relaxation of symmetry constraints compared to direct vibrational coupling.

  8. Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, T. J.; Aker, P. M.; Scharko, N. K.; Williams, S. D.

    2018-02-01

    Using vetted methods for generating quantitative absorption reference data, broadband infrared and near-infrared spectra (total range 11,000 – 600 cm-1) of pyridine vapor were recorded at 0.1 cm-1 spectral resolution, with the analyte thermostatted at 298 K and pressure-broadened to 1 atmosphere using N2 ballast gas. The quantitative spectrum is reported for the first time, and we have re-assigned some of the 27 fundamental modes. Fundamental assignments were confirmed by IR vapor phase band shapes, FT-Raman measurements and comparison with previous analyses. For the 760-Torr vapor-phase IR data several bands show resolved peaks (Q-branches). We have also assigned for the first time hundreds of combination and overtone bands in the mid- and near-IR. All assignments were made via comparison to theoretically calculated frequencies and intensities: The frequencies were computed with Gaussian03 with the anharmonic option, using MP2 and the ccpvtz basis set. The intensities were taken from a VSCF calculation in GAMESS using Hartree-Fock (for overtones and combination bands) or from the harmonic MP2 for fundamentals. Overtone and combination band harmonic and anharmonic frequencies, as well as intensities were also calculated using the CFOUR program. It is seen in the NIR spectrum near 6000 cm-1 that the very strong bands arise from the C-H first overtones, whereas only much weaker bands are observed for combination bands of C-H stretching modes. Certain features are discussed for their potential utility for atmospheric monitoring.

  9. Synthesis, characterization and vibrational spectra analysis of ethyl (2Z)-2-(2-amino-4-oxo-1,3-oxazol-5(4H)-ylidene)-3-oxo-3-phenylpropanoate

    Science.gov (United States)

    Kıbrız, İbrahim Evren; Sert, Yusuf; Saçmacı, Mustafa; Şahin, Ertan; Yıldırım, İsmail; Ucun, Fatih

    2013-10-01

    In the present study, the experimental and theoretical vibrational spectra of ethyl (2Z)-2-(2-amino-4-oxo-1,3-oxazol-5(4H)-ylidene)-3-oxo-3-phenylpropanoate (AOX) were investigated. The experimental FT-IR (400-4000 cm-1) and Laser-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths, bond angles and torsion angles) were calculated using ab initio Hartree Fock (HF), Density Functional Theory (B3LYP and B3PW91) methods with 6-311++G(d,p) basis set by Gaussian 03 program, for the first time. The computed values of frequencies are scaled using a suitable scale factor to yield good coherence with the observed values. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental X-ray diffraction data, and they were seen to be in a good agreement with each other. The hydrogen bonding geometry of the molecule was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

  10. Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d0 and Si-d3.

    Science.gov (United States)

    Durig, James R; Pan, Chunhua; Guirgis, Gamil A

    2003-03-15

    The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2

  11. Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of n-propylsilane-d 0 and Si-d 3

    Science.gov (United States)

    Durig, James R.; Pan, Chunhua; Guirgis, Gamil A.

    2003-03-01

    The infrared (3100-40 cm -1) and Raman (3100-20 cm -1) spectra of gaseous and solid n-propylsilane, CH 3CH 2CH 2SiH 3 and the Si-d 3 isotopomer, CH 3CH 2CH 2SiD 3, have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 °C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220±22 cm -1 (2.63±0.26 kJ mol -1) with the anti conformer the more stable form. A similar value of 234±23 cm -1 (2.80±0.28 kJ mol -1) was obtained for Δ H for the Si-d 3 isotopomer. At ambient temperature it is estimated that there is 30±2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm -1 for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d 0 and Si-d 3 molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d,p) and 6-311+G(2d,2p) basis sets. From the isolated

  12. The 'partial resonance' of the ring in the NLO crystal melaminium formate: study using vibrational spectra, DFT, HOMO-LUMO and MESP mapping.

    Science.gov (United States)

    Binoy, J; Marchewka, M K; Jayakumar, V S

    2013-03-01

    The molecular geometry and vibrational spectral investigations of melaminium formate, a potential material known for toxicity and NLO activity, has been performed. The FT IR and FT Raman spectral investigations of melaminium formate is performed aided by the computed spectra of melaminium formate, triazine, melamine, melaminium and formate ion, along with bond orders and PED, computed using the density functional method (B3LYP) with 6-31G(d) basis set and XRD data, to reveal intermolecular interactions of amino groups with neighbor formula units in the crystal, intramolecular H⋯H repulsion of amino group hydrogen with protonating hydrogen, consequent loss of resonance in the melaminium ring, restriction of resonance to N(3)C(1)N(1) moiety leading to special type resonance of the ring and the resonance structure of CO(2) group of formate ion. The 3D matrix of hyperpolarizability tensor components has been computed to quantify NLO activity of melamine, melaminium and melaminium formate and the hyperpolarizability enhancement is analyzed using computed plots of HOMO and LUMO orbitals. A new mechanism of proton transfer responsible for NLO activity has been suggested, based on anomalous IR spectral bands in the high wavenumber region. The computed MEP contour maps have been used to analyze the interaction of melaminium and formate ions in the crystal. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. The `partial resonance' of the ring in the NLO crystal melaminium formate: Study using vibrational spectra, DFT, HOMO-LUMO and MESP mapping

    Science.gov (United States)

    Binoy, J.; Marchewka, M. K.; Jayakumar, V. S.

    2013-03-01

    The molecular geometry and vibrational spectral investigations of melaminium formate, a potential material known for toxicity and NLO activity, has been performed. The FT IR and FT Raman spectral investigations of melaminium formate is performed aided by the computed spectra of melaminium formate, triazine, melamine, melaminium and formate ion, along with bond orders and PED, computed using the density functional method (B3LYP) with 6-31G(d) basis set and XRD data, to reveal intermolecular interactions of amino groups with neighbor formula units in the crystal, intramolecular H⋯H repulsion of amino group hydrogen with protonating hydrogen, consequent loss of resonance in the melaminium ring, restriction of resonance to N3C1N1 moiety leading to special type resonance of the ring and the resonance structure of CO2 group of formate ion. The 3D matrix of hyperpolarizability tensor components has been computed to quantify NLO activity of melamine, melaminium and melaminium formate and the hyperpolarizability enhancement is analyzed using computed plots of HOMO and LUMO orbitals. A new mechanism of proton transfer responsible for NLO activity has been suggested, based on anomalous IR spectral bands in the high wavenumber region. The computed MEP contour maps have been used to analyze the interaction of melaminium and formate ions in the crystal.

  14. A dual spectroscopic fluorescence probe based on carbon dots for detection of 2,4,6-trinitrophenol/Fe (III) ion by fluorescence and frequency doubling scattering spectra and its analytical applications.

    Science.gov (United States)

    Xu, Jinxia; Bai, Zhangjun; Zu, Fanlin; Yan, Fanyong; Wei, Junfu; Zhang, Saihui; Luo, Yunmei

    2018-07-05

    A convenient, highly sensitive and reliable assay for 2,4,6‑trinitrophenol (TNP) and Fe (III) ion (Fe 3+ ) in the dual spectroscopic manner is developed based on novel carbon dots (CDs). The CDs with highly blue emitting fluorescent were easily prepared via the one-step potassium hydroxide-assisted reflux method from dextrin. The as-synthesized CDs exhibited the high crystalline quality, the excellent fluorescence characteristics with a high quantum yield of ~13.1%, and the narrow size distribution with an average diameter of 6.3±0.5nm. Fluorescence and frequency doubling scattering (FDS) spectra of CDs show the unique changes in the presence of TNP/Fe 3+ by different mechanism. The fluorescence of CDs decreased apparently in the presence of TNP via electron-transfer. Thus, after the experimental conditions were optimized, the linear range for detection TNP is 0-50μM, the detection limit was 19.1nM. With the addition of Fe 3+ , the FDS of CDs appeared to be highly sensitive with a quick response to Fe 3+ as a result of the change concentration of the scattering particle. The emission peak for FDS at 450nm was enhanced under the excitation wavelength at 900nm. The fluorescence response changes linearly with Fe 3+ concentration in the range of 8-40μM, the detection limits were determined to be 44.1nM. The applications of CDs were extended for the detection of TNP, Fe 3+ in real water samples with a high recovery. The results reported here may become the potential tools for the fast response of TNP and Fe 3+ in the analysis of environmental pollutants. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene II. 3,3-Dimethyl-1,2-bis(trimethylsilyl)cyclopropene

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-07-01

    The IR and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene (I) (synthesised using standard procedures) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF/6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors used previously for 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene (17 scale factors for a 105-dimensional problem). The scaled QMFF obtained was used to solve the vibrational problem. The quantum mechanical values of the Raman activities were converted to differential Raman cross sections. The figures for the experimental and theoretical Raman and IR spectra are presented. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distribution and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values (including Raman cross sections) calculated using the unscaled QMFF.

  16. Fluorescence imaging spectroscopy (FIS) for comparing spectra from corn ears naturally and artificially infected with aflatoxin producing fungus.

    Science.gov (United States)

    Hruska, Zuzana; Yao, Haibo; Kincaid, Russell; Darlington, Dawn; Brown, Robert L; Bhatnagar, Deepak; Cleveland, Thomas E

    2013-08-01

    In an effort to address the problem of rapid detection of aflatoxin in grain, particularly oilseeds, the current study assessed the spectral differences of aflatoxin production in kernels from a cornfield inoculated with spores from 2 different strains of toxigenic Aspergillus flavus. Aflatoxin production in corn from the same field due to natural infestation was also assessed. A small corn plot in Baton Rouge, La., U.S.A., was used during the 2008-growing season. Two groups of 400 plants were inoculated with 2 different inocula and 1 group of 400 plants was designated as controls. Any contamination detected in the controls was attributed to natural infestation. A subset of each group was imaged with a visible near infra red (VNIR) hyperspectral system under ultra violet (UV) excitation and subsequently analyzed for aflatoxin using affinity column fluorometry. Group differences were statistically analyzed. Results indicate that when all the spectral data across all groups were averaged, any potential differences between groups (treated and untreated) were obscured. However, spectral analysis based on contaminated "hot" pixel classification showed a distinct spectral shift/separation between contaminated and clean ears with fluorescence peaks at 501 and 478 nm, respectively. All inoculated and naturally infected control ears had fluorescence peaks at 501 nm that differed from uninfected corn ears. Results from this study may be useful in evaluating rapid, noninvasive instrumentation and/or methodology for aflatoxin detection in grain. © 2013 Institute of Food Technologists®

  17. Vibrational Coupling in Conjugated π Systems with a view to Optimization of Fluorescence Yield through Phonon Confinement

    OpenAIRE

    O'Neill, Luke; Lynch, Patrick; McNamara, Mary; Byrne, Hugh J.

    2005-01-01

    A series of π conjugated systems were studied by absorption, photoluminescence and vibrational spectroscopy. As is common for these systems, a linear relationship between the positioning of the absorption and photoluminescence maxima plotted against inverse conjugation length is observed. The relationships are in good agreement with the simple particle in a box method, one of the earliest descriptions of the properties of one-dimensional organic molecules. In addition to the electronic transi...

  18. Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

    Science.gov (United States)

    Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

    2014-03-01

    Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

  19. Vibrational Spectra of Tetrahedral Fullerenes.

    Science.gov (United States)

    Cheng; Li; Tang

    1999-01-01

    From the topological structures of the following classes of tetrahedral fullerenes-(1) Cn(h, h; -i, i), Cn(h, 0; -i, 2i), Cn(2h + i, -h + i; i, i), Cn(h - i, h + 2i; -i, 2i), and Cn(h, i; 0, i) for Td symmetry; (2) Cn(h, k; k, h), Cn(h, k; -h - k, k), and Cn(h, k; -h, h + k) for Th symmetry; (3) Cn(h, k; i, j) for T symmetry-we have obtained theoretically the formulas for the numbers of their IR and Raman active modes for all of the tetrahedral fullerenes through the decomposition of their nuclear motions into irreducible representations by means of group theory. Copyright 1999 Academic Press.

  20. A vacuum-UV laser-induced fluorescence experiment for measurement of rotationally and vibrationally excited H2

    NARCIS (Netherlands)

    Vankan, P.J.W.; Heil, S.B.S.; Mazouffre, S.; Engeln, R.A.H.; Schram, D.C.; Döbele, H.F.

    2004-01-01

    An experimental setup is built to detect spatially resolved rovibrationally excited hydrogen molecules via laser-induced fluorescence. To excite the hydrogen molecules, laser radiation is produced in the vacuum UV part of the spectrum. The laser radiation is tunable between 120 nm and 230 nm and has

  1. Solvent effect in implicit/explicit model on FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra, linear, second- and third-nonlinear optical parameters of 2-(trifluoromethyl)benzoic acid: Experimental and computational study

    Science.gov (United States)

    Avcı, Davut; Altürk, Sümeyye; Tamer, Ömer; Kuşbazoğlu, Mustafa; Atalay, Yusuf

    2017-09-01

    FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra for 2-(trifluoromethyl)benzoic acid (2-TFMBA) were recorded. DFT//B3LYP/6-31++G(d,p) calculations were used to determine the optimized molecular geometry, vibrational frequencies, 1H, 13C and 19F GIAO-NMR chemical shifts of 2-TFMBA. The detailed assignments of vibrational frequencies were carried out on the basis of potential energy distribution (PED) by using VEDA program. TD-DFT/B3LYP/6-31++G(d,p) calculations with the PCM (polarizable continuum model) in ethanol and DMSO solvents based on implicit/explicit model and gas phase in the excited state were employed to investigate UV-vis absorption and fluorescence emission wavelengths. The UV-vis and emission spectra were given in ethanol and DMSO solvents, and the major contributions to the electronic transitions were obtained. In addition, the NLO parameters (β, γ and χ(3)) and frontier molecular orbital energies of 2-TFMBA were calculated by using B3LYP/6-31++G(d,p) level. The NLO parameters of 2-TFMBA were compared with that of para-Nitroaniline (pNA) and urea which are the typical NLO materials. The refractive index (n) is calculated by using the Lorentz-Lorenz equation to observe polarization behavior of 2-TFMBA in DMSO and ethanol solvents. In order to investigate intramolecular and hydrogen bonding interactions, NBO calculations were also performed by the same level. To sum up, considering the well-known biological role, photochemical properties of 2-TFMBA were discussed.

  2. Detection of Copper (II) and Cadmium (II) binding to dissolved organic matter from macrophyte decomposition by fluorescence excitation-emission matrix spectra combined with parallel factor analysis

    International Nuclear Information System (INIS)

    Yuan, Dong-hai; Guo, Xu-jing; Wen, Li; He, Lian-sheng; Wang, Jing-gang; Li, Jun-qi

    2015-01-01

    Fluorescence excitation-emission matrix (EEM) spectra coupled with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM) derived from macrophyte decomposition, and to study its complexation with Cu (II) and Cd (II). Both the protein-like and the humic-like components showed a marked quenching effect by Cu (II). Negligible quenching effects were found for Cd (II) by components 1, 5 and 6. The stability constants and the fraction of the binding fluorophores for humic-like components and Cu (II) can be influenced by macrophyte decomposition of various weight gradients in aquatic plants. Macrophyte decomposition within the scope of the appropriate aquatic phytomass can maximize the stability constant of DOM-metal complexes. A large amount of organic matter was introduced into the aquatic environment by macrophyte decomposition, suggesting that the potential risk of DOM as a carrier of heavy metal contamination in macrophytic lakes should not be ignored. - Highlights: • Macrophyte decomposition increases fluorescent DOM components in the upper sediment. • Protein-like components are quenched or enhanced by adding Cu (II) and Cd (II). • Macrophyte decomposition DOM can impact the affinity of Cu (II) and Cd (II). • The log K M and f values showed a marked change due to macrophyte decomposition. • Macrophyte decomposition can maximize the stability constant of DOM-Cu (II) complexes. - Macrophyte decomposition DOM can influence on the binding affinity of metal ions in macrophytic lakes

  3. Effects of high pressure on the fluorescence spectra of Cr sup 3 sup + in GdAlO sub 3

    CERN Document Server

    Jovanic, B R

    1998-01-01

    The effect of high hydrostatic pressure, up to 100 kbar, on the emission spectra of Cr sup 3 sup + ions in GdAlO sub 3 hosts was studied. A linear shifting (red-shift) of the single-ion line (the R line), the left-hand side (LS) line, right-hand side (RS) line and the neighbouring-pair line (NPL) was observed. The R line shows a pressure-induced shift of 0.082 nm kbar sup - sup 1 , nearly 2.25 times that of ruby. The LS line, RS line and NPL show pressure-induced shifts of 0.0779 nm kbar sup - sup 1 , 0.0864 nm kbar sup - sup 1 and 0.0933 nm kbar sup - sup 1 , respectively. (author)

  4. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra.

    Science.gov (United States)

    Basavaraja, Jana; Suresh Kumar, H M; Inamdar, S R; Wari, M N

    2016-02-05

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π→π⁎ transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μ(e)). It is observed that dipole moment value of excited state (μ(e)) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state. Copyright © 2015. Published by Elsevier B.V.

  5. X-ray scattering in X-ray fluorescence spectra with X-ray tube excitation - Modelling, experiment, and Monte-Carlo simulation

    International Nuclear Information System (INIS)

    Hodoroaba, V.-D.; Radtke, M.; Vincze, L.; Rackwitz, V.; Reuter, D.

    2010-01-01

    X-ray scattering may contribute significantly to the spectral background of X-ray fluorescence (XRF) spectra. Based on metrological measurements carried out with a scanning electron microscope (SEM) having attached a well characterised X-ray source (polychromatic X-ray tube) and a calibrated energy dispersive X-ray spectrometer (EDS) the accuracy of a physical model for X-ray scattering is systematically evaluated for representative samples. The knowledge of the X-ray spectrometer efficiency, but also of the spectrometer response functions makes it possible to define a physical spectral background of XRF spectra. Background subtraction relying on purely mathematical procedures is state-of-the-art. The results produced by the analytical model are at least as reliable as those obtained by Monte-Carlo simulations, even without considering the very challenging contribution of multiple scattering. Special attention has been paid to Compton broadening. Relevant applications of the implementation of the analytical model presented in this paper are the prediction of the limits of detection for particular cases or the determination of the transmission of X-ray polycapillary lenses.

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

    Science.gov (United States)

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

    2013-01-15

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

  7. Calculated rotational and vibrational g factors of LiH X 1S+ and evaluation of parameters in radial functions from rotational and vibration-rotational spectra

    DEFF Research Database (Denmark)

    Sauer, Stephan P. A.; Paidarová, Ivana; Oddershede, Jens

    2011-01-01

    The vibrational g factor, that is, the nonadiabatic correction to the vibrational reduced mass, of LiH has been calculated for internuclear distances over a wide range. Based on multiconfigurational wave functions with a large complete active space and an extended set of gaussian type basis...

  8. A vacuum-UV laser-induced fluorescence experiment for measurement of rotationally and vibrationally excited H2

    International Nuclear Information System (INIS)

    Vankan, P.; Heil, S.B.S.; Mazouffre, S.; Engeln, R.; Schram, D.C.; Doebele, H.F.

    2004-01-01

    An experimental setup is built to detect spatially resolved rovibrationally excited hydrogen molecules via laser-induced fluorescence. To excite the hydrogen molecules, laser radiation is produced in the vacuum UV part of the spectrum. The laser radiation is tunable between 120 nm and 230 nm and has a bandwith of 0.15 cm -1 . The wavelength of the laser radiation is calibrated by simultaneous recording of the two-photon laser induced fluorescence spectrum of nitric oxide. The excited hydrogen populations are calibrated on the basis of coherent anti-Stokes Raman scattering measurements. A population distribution is measured in the shock region of a pure hydrogen plasma expansion. The higher rotational levels (J>5) show overpopulation compared to a Boltzmann distribution determined from the lower rotational levels (J≤5)

  9. Calculation of vibrational spectra of complex hydrides, LiBeH/sub 3/, NaBeH/sub 3/ and LiMgH/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Sukhanov, L P; Boldyrev, A I [AN SSSR, Chernogolovka. Inst. Novykh Khimicheskikh Problem

    1984-03-01

    The non-empirical Hartree-Fock-Ruthan method with a two-exponent Ros-Zigban basis has been used to calculate the coefficients of harmonic force field, frequency and intensity of normal vibrations of the LiBeH/sub 3/, NaBeH/sub 3/ and LiMgH/sub 3/ complex hydrides. Attribution of vibrational types is conducted. Isotope shifts for different isotope substitutions in the L(MH/sub 3/) are calculated. The effect of the nature of both the outer-spherical cation L/sup +/ and central atom M on the vibrational spectrum is discussed.

  10. Vibronic spectra of Gd3+ in metaphosphate glasses: Comparison with Raman and infrared spectra

    International Nuclear Information System (INIS)

    Hall, D.W.; Brawer, S.A.; Weber, M.J.

    1982-01-01

    Vibronic sidebands associated with the 6 P/sub 7/2/→ 8 S/sub 7/2/ transition of Gd 3+ -doped metaphosphate glasses are observed using line-narrowed fluorescence techniques. Glasses having metal cations of different mass and charge (La,Al,Mg,Ba) are examined. Vibronic spectra, which probe vibrations about the rare-earth element site, are compared with polarized Raman scattering data and the infrared dielectric constant obtained from near-normal reflectance measurements. Results indicate that in metaphosphate glasses vibronic selection rules are similar to HV (vertical height) Raman selection rules. The wavelengths and relative intensities of peaks in the high-frequency portion of the vibronic spectra change with respect to corresponding peaks in the Raman spectra when the mass and/or charge of Gd 3+ differs significantly from that of the metal cation

  11. A comparative study of MP2, B3LYP, RHF and SCC-DFTB force fields in predicting the vibrational spectra of N-acetyl-L-alanine-N'-methyl amide: VA and VCD spectra

    DEFF Research Database (Denmark)

    Bohr, Henrik; Jalkanen, Karl J.; Elstner, M.

    1999-01-01

    dichroism (VCD) spectra of NALANMA. We have utilised MP2/6-31G*, B3LYP/6-31G*, RHF/6-31G* and SCC-DFTB level theory to determine the geometries and Hessians, atomic polar tensors (APT) and atomic axial tensors (AAT) which are required for simulating the VA and VCD spectra. We have also calculated the AAT...

  12. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene IV. 3,3-Dimethyl-1,2-bis(trimethylgermyl)cyclopropene

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2003-06-01

    The infrared (IR) and Raman spectra of 3,3-dimethyl-1,2-bis(trimethylgermyl)cyclopropene (I) were measured in the liquid phase. Total geometry optimisation was performed at the HF/6-31G* level. The HF/6-31G*//HF6-31G* quantum mechanical force field (QMFF) was calculated and used to determine the theoretical fundamental vibrational frequencies, their predicted IR intensities, Raman activities, and Raman depolarisation ratios. Using Pulay's scaling method and the theoretical molecular geometry, the QMFF of I was scaled by a set of scaling factors comprised of elements transferred from the sets used to correct the QMFF's of 3,3-dimethylbutene-1, and 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene (17 scale factors for a 105-dimensional problem). This set of scale factors was used previously to correct the QMFF of 3,3-dimethyl-1,2-bis(tert-butyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropene. The scaled QMFF obtained was used to solve the vibrational problem. Differential Raman cross-sections were calculated using the quantum mechanical values of the Raman activities. The appropriate theoretical spectrograms for the Raman and IR spectra of I were constructed. Assignments of the experimental vibrational spectra of I are given. They take into account the calculated potential energy distributions and the correlation between the estimations of the experimental IR and Raman intensities and Raman depolarisation ratios and the corresponding theoretical values calculated using the unscaled QMFF.

  13. Enhanced vibration diagnostics using vibration signature analysis

    International Nuclear Information System (INIS)

    Ahmed, S.; Shehzad, K.; Zahoor, Y.; Mahmood, A.; Bibi, A.

    2001-01-01

    Symptoms will appear in equipment, as well as in human beings. when 'suffering from sickness. Symptoms of abnormality in equipment are vibration, noise, deformation, temperature, pressure, electric current, crack, wearing, leakage etc. these are called modes of failure. If the mode of failure is vibration then the vibration signature analysis can be effectively used in order to diagnose the machinery problems. Much valuable information is contained within these vibration 'Spectra' or 'Signatures' but is only of use if the analyst can unlock its 'Secrets'. This paper documents a vibration problem in the motor of a centrifugal pump (Type ETA). It focuses mainly on the roll of modern vibration monitoring system in problem analysis. The problem experienced was the motor unstability and noise due to high vibration. Using enhanced vibration signature data, the problem was analyzed. which suggested that the rotor eccentricity was the cause of excessive noise and vibration in the motor. In conclusion, advanced electronic monitoring and diagnostic systems provide powerful information for machine's condition assessment and problem analysis. Appropriate interpretation and use of this information is important for accurate and effective vibration analysis. (author)

  14. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene . VI: Application of observed trends to stannyl derivatives

    Science.gov (United States)

    Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2004-09-01

    The effects of substitution of X=C by Si or Ge in X(CH 3) 3 moieties attached to the formal double bond of 3,3-dimethylcyclopropene are examined. Regularities in observed trends of vibrational frequencies implicating the moieties containing the X atom, as the X atomic mass is increased, are extrapolated to X=Sn. The results of this extrapolation made it possible to assign the known experimental vibrational frequencies of 3,3-dimethyl-1-(trimethylstannyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylstannyl)cyclopropene.

  15. Spectra and relaxation dynamics of the pseudohalide (PS) vibrational bands for Ru(bpy)2(PS)2 complexes, PS = CN, NCS and N3

    International Nuclear Information System (INIS)

    Compton, Ryan; Gerardi, Helen K.; Weidinger, Daniel; Brown, Douglas J.; Dressick, Walter J.; Heilweil, Edwin J.; Owrutsky, Jeffrey C.

    2013-01-01

    Highlights: ► Static and transient infrared spectroscopy of pseudohalide bipyridine ruthenium complexes. ► Vibrational energy relaxes faster for the azide than the thiocyanate and cyanide analogs. ► Intramolecular vibrational relaxation is prevalent in cis-Ru(bpy) 2 (N 3 ) 2 . - Abstract: Static and transient infrared spectroscopy were used to investigate cis-Ru(bpy) 2 (N 3 ) 2 (bpy = 2,2′-bipyridine), cis-Ru(bpy) 2 (NCS) 2 , and cis-Ru(bpy) 2 (CN) 2 in solution. The NC stretching IR band for cis-Ru(bpy) 2 (NCS) 2 appears at higher frequency (∼2106 cm −1 in DMSO) than for the free NCS − anion while the IR bands for the azide and cyanide complexes are closer to those of the respective free anions. The vibrational energy relaxation (VER) lifetime for the azide complex is found to be much shorter (∼5 ps) than for either the NCS or CN species (both ∼70 ps in DMSO) and the lifetimes resemble those for each corresponding free anion in solution. However, for cis-Ru(bpy) 2 (N 3 ) 2 , it is determined that the transition frequency depends more on the solvent than the VER lifetime implying that intramolecular vibrational relaxation is predominant over solvent energy-extracting interactions. These results are compared to the behavior of other related metal complexes in solution

  16. Crystal structures and vibrational spectra of biuret co-crystals with cyanuric and glutaric acids, discussion of hydrogen bonding involving carbonyl groups

    Czech Academy of Sciences Publication Activity Database

    Matulková, I.; Mathauserová, J.; Císařová, I.; Němec, I.; Fábry, Jan

    2016-01-01

    Roč. 231, č. 5 (2016), s. 291-300 ISSN 2194-4946 R&D Projects: GA ČR GA14-05506S Institutional support: RVO:68378271 Keywords : biuret * crystal structure analysis * hydrogen bonding * vibrational spectroscopy * X-ray diffraction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.179, year: 2016

  17. Numerical-analytic implementation of the higher-order canonical Van Vleck perturbation theory for the interpretation of medium-sized molecule vibrational spectra.

    Science.gov (United States)

    Krasnoshchekov, Sergey V; Isayeva, Elena V; Stepanov, Nikolay F

    2012-04-12

    Anharmonic vibrational states of semirigid polyatomic molecules are often studied using the second-order vibrational perturbation theory (VPT2). For efficient higher-order analysis, an approach based on the canonical Van Vleck perturbation theory (CVPT), the Watson Hamiltonian and operators of creation and annihilation of vibrational quanta is employed. This method allows analysis of the convergence of perturbation theory and solves a number of theoretical problems of VPT2, e.g., yields anharmonic constants y(ijk), z(ijkl), and allows the reliable evaluation of vibrational IR and Raman anharmonic intensities in the presence of resonances. Darling-Dennison and higher-order resonance coupling coefficients can be reliably evaluated as well. The method is illustrated on classic molecules: water and formaldehyde. A number of theoretical conclusions results, including the necessity of using sextic force field in the fourth order (CVPT4) and the nearly vanishing CVPT4 contributions for bending and wagging modes. The coefficients of perturbative Dunham-type Hamiltonians in high-orders of CVPT are found to conform to the rules of equality at different orders as earlier proven analytically for diatomic molecules. The method can serve as a good substitution of the more traditional VPT2.

  18. Calculation of the vibrational linewidth and line shape of Raman spectra using the relaxation function : I. method and application to nitrogen

    NARCIS (Netherlands)

    Kooi, M.E.; Smit, F.; Michels, J.P.J.; Schouten, J.A.

    2000-01-01

    The spectral line shape of the fundamental vibration of nitrogen is calculated from molecular dynamics simulations by determining the Fourier transform of the relaxation function. It has been applied to the fluid phase at various pressures and temperatures, and to solid d-N2. The validity of the

  19. Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethyl cyclopropene V. 3,3-Dimethyl-1-(trimethylgermyl)cyclopropene

    Science.gov (United States)

    De Maré, G. R.; Panchenko, Yu. N.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

    2004-02-01

    3,3-Dimethyl-1-(trimethylgermyl)cyclopropene ( I) was synthesised using a standard procedure. The IR and Raman spectra of I in the liquid phase were measured. The molecular geometry of I was optimised completely at the HF/6-31G* level. The HF/6-31G*//HF/6-31G* force field was calculated and scaled using the set of scale factors transferred from those determined previously for scaling the theoretical force fields of 3,3-dimethylbutene-1 and 1-methyl-, 1,2-dimethyl-, and 3,3-dimethylcyclopropene. The assignments of the observed vibrational bands were performed using the theoretical frequencies calculated from the scaled HF/6-31G*//HF/6-31G* force field and the ab initio values of the IR intensities, Raman cross-sections and depolarisation ratios. The theoretical spectra are given. The completely optimised structural parameters of I and its vibrational frequencies are compared with corresponding data of related molecules.

  20. The fluorescence and resonance Rayleigh scattering spectra study on the interactions of palladium (II)-Nootropic chelate with Congo red and their analytical applications

    Science.gov (United States)

    Chen, Fang; Peng, Jingdong; Liu, Shaopu; Peng, Huanjun; Pan, Ziyu; Bu, Lingli; Xiao, Huan; Zhang, Ruiwen

    2017-04-01

    A highly sensitive detection approach of resonance Rayleigh scattering spectra (RRS) is firstly applied to analyzing nootropic drugs including piracetam (PIR) and oxiracetam (OXI). In HCl-NaAc buffer solution (pH = 3.0), the OXI chelated with palladium (II) to form the chelate cation [Pd2·OXI]2 +, and then reacted with Congo red (CGR) by virtue of electrostatic attraction and hydrophobic force to form binary complex [Pd2·OXI]. CGR2, which could result in the great enhancement of RRS. The resonance Rayleigh scattering signal was recorded at λex = λem = 375 nm. This mixture complex not only has higher RRS, but also makes contribution to significant increase of fluorescence, and the same phenomena also were discovered in PIR. The enhanced RRS intensity is in proportion to the PIR and OXI concentration in the range of 0.03-3.0 μg mL- 1, and the detection limit (DL) of RRS method for PIR and OXI is 2.3 ng mL- 1 and 9.7 ng mL- 1. In addition, the DL of fluorescence method for PIR and OXI is 8.4 μg mL- 1 and 19.5 μg mL- 1. Obviously, the RRS is the highly sensitive method, and the recoveries of the two kinds of nootropic drugs were range from 100.4% to 101.8.0% with RSD (n = 5) from 1.1% to 3.1% by RRS method. This paper not only investigated the optimum conditions for detecting nootropics with using RRS method, but also focused on the reasons for enhancing RRS intensity and the reaction mechanism, which in order to firm and contract the resultant. Finally, The RRS method has been applied to detect nootropic drugs in human urine samples with satisfactory results. Fig. S2. The effect of ionic strength: Pd (II)-CGR system (curve a); Pd (II)-OXI-CGR system (curve b); Pd (II)-PIR- CGR system (curve c). Pd (II): 2.0 × 10- 4 mol L- 1; CGR: 1.0 × 10- 5 mol L- 1; OXI: 1.5 μg mL- 1; PIR: 2 μg mL- 1; NaCl: 1 mol L- 1. Fig. S3. The effect of time: Pd (II)-OXI-CGR system (curve a); Pd (II)-PIR-CGR system (curve b). Pd (II): 2.0 × 10- 4 mol L- 1; CGR: 1.0 × 10- 5 mol L- 1

  1. Calculation and analysis of vibrational spectra of PbCl(2)-Sb(2)O(3)-TeO(2) glass from first principles

    Czech Academy of Sciences Publication Activity Database

    Macháček, J.; Kostka, Petr; Liška, M.; Zavadil, Jiří; Gedeon, O.

    2011-01-01

    Roč. 357, č. 14 (2011), s. 2562-2570 ISSN 0022-3093 R&D Projects: GA ČR GA104/08/0734; GA MPO 2A-1TP1/063 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z20670512 Keywords : vibrational spectrum * tellurite glass * ab initio molecular simulation Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 1.537, year: 2011

  2. 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

  3. Super-multiplex vibrational imaging

    Science.gov (United States)

    Wei, Lu; Chen, Zhixing; Shi, Lixue; Long, Rong; Anzalone, Andrew V.; Zhang, Luyuan; Hu, Fanghao; Yuste, Rafael; Cornish, Virginia W.; Min, Wei

    2017-04-01

    The ability to visualize directly a large number of distinct molecular species inside cells is increasingly essential for understanding complex systems and processes. Even though existing methods have successfully been used to explore structure-function relationships in nervous systems, to profile RNA in situ, to reveal the heterogeneity of tumour microenvironments and to study dynamic macromolecular assembly, it remains challenging to image many species with high selectivity and sensitivity under biological conditions. For instance, fluorescence microscopy faces a ‘colour barrier’, owing to the intrinsically broad (about 1,500 inverse centimetres) and featureless nature of fluorescence spectra that limits the number of resolvable colours to two to five (or seven to nine if using complicated instrumentation and analysis). Spontaneous Raman microscopy probes vibrational transitions with much narrower resonances (peak width of about 10 inverse centimetres) and so does not suffer from this problem, but weak signals make many bio-imaging applications impossible. Although surface-enhanced Raman scattering offers high sensitivity and multiplicity, it cannot be readily used to image specific molecular targets quantitatively inside live cells. Here we use stimulated Raman scattering under electronic pre-resonance conditions to image target molecules inside living cells with very high vibrational selectivity and sensitivity (down to 250 nanomolar with a time constant of 1 millisecond). We create a palette of triple-bond-conjugated near-infrared dyes that each displays a single peak in the cell-silent Raman spectral window; when combined with available fluorescent probes, this palette provides 24 resolvable colours, with the potential for further expansion. Proof-of-principle experiments on neuronal co-cultures and brain tissues reveal cell-type-dependent heterogeneities in DNA and protein metabolism under physiological and pathological conditions, underscoring the

  4. IUPAC critical evaluation of the rotational-vibrational spectra of water vapor. Part I-Energy levels and transition wavenumbers for H217O and H218O

    International Nuclear Information System (INIS)

    Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Carleer, Michel R.; Csaszar, Attila G.; Gamache, Robert R.; Hodges, Joseph T.; Jenouvrier, Alain; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Toth, Robert A.; Vandaele, Ann Carine; Zobov, Nikolai F.; Daumont, Ludovic; Fazliev, Alexander Z.; Furtenbacher, Tibor; Gordon, Iouli E.; Mikhailenko, Semen N.

    2009-01-01

    This is the first part of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependence and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. The present article contains energy levels and data for line positions of the singly substituted isotopologues H 2 17 O and H 2 18 O. The procedure and code MARVEL, standing for measured active rotational-vibrational energy levels, is used extensively in all stages of determining the validated levels and lines and their self-consistent uncertainties. The spectral regions covered for both isotopologues H 2 17 O and H 2 18 O are 0-17125cm -1 . The energy levels are checked against ones determined from accurate variational calculations. The number of critically evaluated and recommended levels and lines are, respectively, 2687 and 8614 for H 2 17 O, and 4839 and 29 364 for H 2 18 O. The extensive lists of MARVEL lines and levels obtained are deposited in the Supplementary Material, as well as in a distributed information system applied to water, W-DIS, where they can easily be retrieved. A distinguishing feature of the present evaluation of water spectroscopic data is the systematic use of all available experimental data and validation by first-principles theoretical calculations.

  5. Crystallographic data and vibrational spectra of some tellurium containing perovskites of the type A/sub 3/sup(II)B/sub 2/sup(III)TeO/sub 9/

    Energy Technology Data Exchange (ETDEWEB)

    Botto, I L; Baran, E J [La Plata Univ. Nacional (Argentina). Facultad de Ciencias Exactas

    1981-02-01

    The preparation of some new mixed oxides, of the type Sr/sub 3/M/sub 2/TeO/sub 9/ (M = Al, Ga, In) and Ca/sub 3/M/sub 2/TeO/sub 9/ (M = Al, Ga, In, Co, Fe, Cr) is described, which are structurally related to the perovskite. The unit cell parameters of these phases have been determined from the corresponding powder diagrams. The vibrational spectra are recorded and assigned and the force constants for the TeO/sub 6/ units present in these lattices are calculated. It is also shown, that the incorporation of trivalent lanthanide cations in these systems is only possible in a limited extent.

  6. 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.

  7. Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

    Science.gov (United States)

    Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

    2015-12-01

    Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

  8. Antagonistic properties of a natural product-Bicuculline with the gamma-aminobutyric acid receptor: studied through electrostatic potential mapping, electronic and vibrational spectra using ab initio and density functional theory.

    Science.gov (United States)

    Srivastava, Anubha; Tandon, Poonam; Jain, Sudha; Asthana, B P

    2011-12-15

    (+)-Bicuculline (hereinafter referred to as bicuculline), a phthalide isoquinoline alkaloid is of current interest as an antagonist of gamma-aminobutyric acid (GABA). Its inhibitor properties have been studied through molecular electrostatic potential (MEP) mapping of this molecule and GABA receptor. The hot site on the potential surface of bicuculline, which is also isosteric with GABA receptor, has been used to interpret the inhibitor property. A systematic quantum chemical study of the possible conformations, their relative stabilities, FT-Raman, FT-IR and UV-vis spectroscopic analysis of bicuculline has been reported. The optimized geometries, wavenumber and intensity of the vibrational bands of all the conformers of bicuculline have been calculated using ab initio Hartree-Fock (HF) and density functional theory (DFT) employing B3LYP functional and 6-311G(d,p) basis set. Mulliken atomic charges, HOMO-LUMO gap ΔE, ionization potential, dipole moments and total energy have also been obtained for the optimized geometries of both the molecules. TD-DFT method is used to calculate the electronic absorption parameters in gas phase as well as in solvent environment using integral equation formalism-polarizable continuum model (IEF-PCM) employing 6-31G basis set and the results thus obtained are compared with the UV absorption spectra. The combination of experimental and calculated results provides an insight into the structural and vibrational spectroscopic properties of bicuculline. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Vibrational spectra and lattice instabilities in the high-T/sub c/ superconductors YBa2Cu3O7 and GdBa2Cu3O7

    International Nuclear Information System (INIS)

    Bozovic, I.; Mitzi, D.; Beasley, M.

    1987-01-01

    The exceptionally high T/sub c/ of layered cuprates was proposed recently as originating from electronically driven structural instabilities. We have studied the infrared and Raman spectra of YBa 2 Cu 3 O/sub 7-//sub δ/ and GdBa 2 Cu 3 O/sub 7-//sub δ/ over a broad range of temperatures, from 10 to 300 K. We observed neither mode softening nor any other spectroscopic signature of lattice instabilities

  10. Molecular Structure, Vibrational Spectra, Quantum Chemical Calculations and Photochemistry of Picolinamide and Isonicotinamide Isolated in Cryogenic Inert Matrixes and in the Neat Low-Temperature Solid Phases

    OpenAIRE

    Borba, Ana; Gómez-Zavaglia, Andrea; Fausto, R.

    2007-01-01

    Picolinamide (PA) and isonicotinamide (INA), two structural isomers of pyridinecarboxamide, have been investigated by matrix isolation and low-temperature solid-state infrared spectroscopy, combined with UV (λ > 235 nm) photoexcitation and density functional theory and ab initio (MP2) theoretical studies. In consonance with the theoretical data, both PA and INA were found to exist in a single conformation in cryogenic rare gas matrixes. Comparison between the experimental spectra of the matri...

  11. Molecular structure, vibrational spectra, MEP, HOMO-LUMO and NBO analysis of Hf(SeO3)(SeO4)(H2O)4

    Science.gov (United States)

    Yankova, Rumyana; Genieva, Svetlana; Halachev, Nenko; Dimitrova, Ginka

    2016-02-01

    Hf(SeO3)(SeO4)(H2O)4 was obtained with the hydrothermal synthesis. The geometry optimization of this molecule was done by Density Functional Theory (DFT/B3LYP) method with 6-31G(d) basis set and LANL2DZ for Hf. The experimental infrared spectrum was compared with calculated and complete vibrational assignment was provided. The bond orders and the electronic properties of the molecule were calculated. The natural bond orbital analysis (NBO) was performed in order to study the intramolecular bonding interactions among bonds and delocalization of unpaired electrons. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap were presented. The electrostatic potential was calculated in order to investigate the reaction properties of the molecule. The thermodynamic properties of the studied compound at different temperatures were calculated.

  12. 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.

  13. The vibrational spectra of some tetrachlorides in rare gas matrices with particular reference to the molecular shapes of ThCl4 and UCl4

    International Nuclear Information System (INIS)

    Arthers, S.A.; Beattie, I.R.

    1984-01-01

    Infrared spectra of tin, lead, hafnium, thorium, and uranium tetrachlorides isolated in inert gas matrices are reported. The results obtained for the tin, lead, and hafnium compounds follow the expected isotope patterns for a tetrahedral molecule except for the observation of additional weak features to high frequency of the all- 35 Cl isotopomers. By contrast for thorium tetrachloride the observed spectrum is not characteristic of a Tsub(d) molecule but can be fitted to a species with Csub(2v) symmetry. Similar results (although less detailed) were obtained for uranium tetrachloride. (author)

  14. Identification of new fluorescence processes in the UV spectra of cool stars from new energy levels of Fe II and Cr II

    Science.gov (United States)

    Johansson, Sveneric; Carpenter, Kenneth G.

    1988-01-01

    Two fluorescence processes operating in atmospheres of cool stars, symbiotic stars, and the Sun are presented. Two emission lines, at 1347.03 and 1360.17 A, are identified as fluorescence lines of Cr II and Fe II. The lines are due to transitions from highly excited levels, which are populated radiatively by the hydrogen Lyman alpha line due to accidental wavelength coincidences. Three energy levels, one in Cr II and two in Fe II, are reported.

  15. Proton and electron impact on molecular and atomic oxygen: I. High resolution fluorescence spectra in the visible and VUV spectral range and emission cross-sections for dissociative ionisation and excitation of O2

    International Nuclear Information System (INIS)

    Wilhelmi, O.; Schartner, K.H.

    2000-01-01

    For pt.II see ibid., vol.11, p.45-58, 2000. Molecular oxygen O 2 was dissociated in collisions with protons and electrons in the intermediate velocity range (p + -energies: 17-800 keV, e - -energies: 0.2-2 keV). Fluorescence from excited atomic and singly ionised fragments and from singly ionised molecules was detected in the VUV and in the visible and near UV spectral range. Highly resolved spectra are presented for the VUV (46-131 nm) and the near UV/visible (340-605 nm) spectral range. Absolute emission cross-sections have been determined for dissociative ionisation and excitation leading to fluorescence in the VUV. Results are compared with published data. (orig.)

  16. Atomic beams probe surface vibrations

    International Nuclear Information System (INIS)

    Robinson, A.L.

    1982-01-01

    In the last two years, surface scientist have begun trying to obtain the vibrational frequencies of surface atoms in both insulating and metallic crystals from beams of helium atoms. It is the inelastic scattering that researchers use to probe surface vibrations. Inelastic atomic beam scattering has only been used to obtain vibrational frequency spectra from clean surfaces. Several experiments using helium beams are cited. (SC)

  17. IUPAC critical evaluation of the rotational–vibrational spectra of water vapor. Part IV. Energy levels and transition wavenumbers for D216O, D217O, and D218O

    International Nuclear Information System (INIS)

    Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Császár, Attila G.; Daumont, Ludovic; Gamache, Robert R.; Hodges, Joseph T.; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Vandaele, Ann Carine; Zobov, Nikolai F.; Dénes, Nóra; Fazliev, Alexander Z.

    2014-01-01

    This paper is the fourth of a series of papers reporting critically evaluated rotational–vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This paper presents energy level and transition data for the following doubly and triply substituted isotopologues of water: D 2 16 O, D 2 17 O, and D 2 18 O. The MARVEL (Measured Active Rotational–Vibrational Energy Levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0–14 016, 0–7969, and 0–9108 cm −1 for D 2 16 O, D 2 17 O, and D 2 18 O, respectively. For D 2 16 O, D 2 17 O, and D 2 18 O, 53 534, 600, and 12 167 lines are considered, respectively, from spectra recorded in absorption at room temperature and in emission at elevated temperatures. The number of validated energy levels is 12 269, 338, and 3351 for D 2 16 O, D 2 17 O, and D 2 18 O, respectively. The energy levels have been checked against the ones determined, with an average accuracy of about 0.03 cm −1 , from variational rovibrational computations employing exact kinetic energy operators and an accurate potential energy surface. Furthermore, the rovibrational labels of the energy levels have been validated by an analysis of the computed wavefunctions using the rigid-rotor decomposition (RRD) scheme. The extensive list of MARVEL lines and levels obtained is deposited in the Supplementary Material of this paper, in a distributed information system applied to water, W@DIS, and on the official MARVEL website, where they can easily be retrieved. - Highlights: • All published transitions are collected and analyzed. • A set of validated rovibrational transitions are presented. • Experimental energy levels for all three D 2 O isotopologues are determined. • Synthetic spectra are presented using these validated energy levels

  18. The Rovibronic Spectra of the Cyclopentadienyl Radical

    Science.gov (United States)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  19. Vibrational and UV spectroscopic studies of 2-coumaranone by experimental and density functional theory calculations

    Science.gov (United States)

    Priya, Y. Sushma; Rao, K. Ramachandra; Chalapathi, P. V.; Satyavani, M.; Veeraiah, A.

    2017-09-01

    The vibrational and electronic properties of 2-coumaranone have been reported in the ground state using experimental techniques (FT-IR, FT-Raman, UV spectra and fluorescence microscopic imaging) and density functional theory (DFT) employing B3LYP correlation with the 6-31G(d, p) basis set. The theoretically reported optimized parameters, vibrational frequencies etc., were compared with the experimental values, which yielded good concurrence between the experimental and calculated values. The assignments of the vibrational spectra were done with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field(SQMFF) methodology. The whole assignments of fundamental modes were based on the potential energy distribution (PED) matrix. The electric dipole moment and the first order hyperpolarizability of the 2-coumaranone have been computed using quantum mechanical calculations. NBO and HOMO, LUMO analyses have been carried out. UV spectrum of 2-coumaranone was recorded in the region 100-300 nm and compared with the theoretical UV spectrum using TD-DFT and SAC-CI methods by which a good agreement is observed. Fluorescence microscopic imaging study reflects that the compound fluoresces in the green-yellow region.

  20. OH vibrational activation and decay dynamics of CH4-OH entrance channel complexes

    International Nuclear Information System (INIS)

    Wheeler, Martyn D.; Tsiouris, Maria; Lester, Marsha I.; Lendvay, Gyoergy

    2000-01-01

    Infrared spectroscopy has been utilized to examine the structure and vibrational decay dynamics of CH 4 -OH complexes that have been stabilized in the entrance channel to the CH 4 +OH hydrogen abstraction reaction. Rotationally resolved infrared spectra of the CH 4 -OH complexes have been obtained in the OH fundamental and overtone regions using an IR-UV (infrared-ultraviolet) double-resonance technique. Pure OH stretching bands have been identified at 3563.45(5) and 6961.98(4) cm-1 (origins), along with combination bands involving the simultaneous excitation of OH stretching and intermolecular bending motions. The infrared spectra exhibit extensive homogeneous broadening arising from the rapid decay of vibrationally activated CH 4 -OH complexes due to vibrational relaxation and/or reaction. Lifetimes of 38(5) and 25(3) ps for CH 4 -OH prepared with one and two quanta of OH excitation, respectively, have been extracted from the infrared spectra. The nascent distribution of the OH products from vibrational predissociation has been evaluated by ultraviolet probe laser-induced fluorescence measurements. The dominant inelastic decay channel involves the transfer of one quantum of OH stretch to the pentad of CH 4 vibrational states with energies near 3000 cm-1. The experimental findings are compared with full collision studies of vibrationally excited OH with CH 4 . In addition, ab initio electronic structure calculations have been carried out to elucidate the minimum energy configuration of the CH 4 -OH complex. The calculations predict a C 3v geometry with the hydrogen of OH pointing toward one of four equivalent faces of the CH 4 tetrahedron, consistent with the analysis of the experimental infrared spectra. (c) 2000 American Institute of Physics

  1. Infrared Spectra of the 10-μm Bands of 1,2-Difluoroethane and 1,1,2-Trifluoroethane: Vibrationally Mediated Torsional Tunneling in 1,1,2-Trifluoroethane

    Science.gov (United States)

    Stone, Stephen C.; Miller, C. Cameron; Philips, Laura A.; Andrews, A. M.; Fraser, G. T.; Pate, B. H.; Xu, Li-Hong

    1995-12-01

    The 3-MHz-resolution infrared spectra of the 10-μm bands of thegaucheconformer of 1,2-difluoroethane (HFC152) and theC1-symmetry conformer of 1,1,2-trifluoroethane (HFC143) have been measured using a molecular-beam electric-resonance optothermal spectrometer with a tunable microwave-sideband CO2laser source. For 1,2-difluoroethane, two bands have been studied, the ν17B-symmetry C-F stretch at 1077.3 cm-1and the ν13B-symmetry CH2rock at 896.6 cm-1. Both bands are well fit to a asymmetric-rotor Hamiltonian to better than 0.5 MHz. The ν13band is effectively unperturbed, while the ν17band is weakly perturbed, as shown by the large change in centrifugal distortion constants from the ground state values. Two bands have also been studied for 1,1,2-trifluoroethane, the ν11symmetric CF2stretch at 1077.2 cm-1and the ν13C-C stretch at 905.1 cm-1. One of the two bands, ν11, is unperturbed and fit to near the experimental precision. The ν13vibration, on the other hand, is weakly perturbed by an interaction with a nearby state. This perturbation leads to a doubling or splitting of the lines, due to a perturbation-induced lifting of the degeneracy of the symmetric and antisymmetric tunneling states associated with tunneling between the two equivalentC1forms. For theJ,Kastates studied, the splittings are as large as 37 MHz. Combining this observation with published low-resolution far-infrared measurements of torsional sequence-band and hot-band frequencies and calculations from an empirical torsional potential allows us to identify the perturbing state as ν17+ 6ν18. Here, ν17is the CF2twist and ν18is the torsion. The matrix element responsible for this interaction exchanges eight vibrational quanta!

  2. Vibrational investigation on FT-IR and FT-Raman spectra, IR intensity, Raman activity, peak resemblance, ideal estimation, standard deviation of computed frequencies analyses and electronic structure on 3-methyl-1,2-butadiene using HF and DFT (LSDA/B3LYP/B3PW91) calculations.

    Science.gov (United States)

    Ramalingam, S; Jayaprakash, A; Mohan, S; Karabacak, M

    2011-11-01

    FT-IR and FT-Raman (4000-100 cm(-1)) spectral measurements of 3-methyl-1,2-butadiene (3M12B) have been attempted in the present work. Ab-initio HF and DFT (LSDA/B3LYP/B3PW91) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, IR intensities and Raman activities. Complete vibrational assignments on the observed spectra are made with vibrational frequencies obtained by HF and DFT (LSDA/B3LYP/B3PW91) at 6-31G(d,p) and 6-311G(d,p) basis sets. The results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The potential energy distribution (PED) corresponding to each of the observed frequencies are calculated which confirms the reliability and precision of the assignment and analysis of the vibrational fundamentals modes. The oscillation of vibrational frequencies of butadiene due to the couple of methyl group is also discussed. A study on the electronic properties such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties of the title compound at different temperatures reveal the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H). Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  3. Multimodal fluorescence imaging spectroscopy

    NARCIS (Netherlands)

    Stopel, Martijn H W; Blum, Christian; Subramaniam, Vinod; Engelborghs, Yves; Visser, Anthonie J.W.G.

    2014-01-01

    Multimodal fluorescence imaging is a versatile method that has a wide application range from biological studies to materials science. Typical observables in multimodal fluorescence imaging are intensity, lifetime, excitation, and emission spectra which are recorded at chosen locations at the sample.

  4. Fluorescence-excitation and emission spectra from LH2 antenna complexes of Rhodopseudomonas acidophila as a function of the sample preparation conditions.

    Science.gov (United States)

    Kunz, Ralf; Timpmann, Kõu; Southall, June; Cogdell, Richard J; Köhler, Jürgen; Freiberg, Arvi

    2013-10-10

    The high sensitivity of optical spectra of pigment-protein complexes to temperature and pressure is well known. In the present study, we have demonstrated the significant influence of the environments commonly used in bulk and single-molecule spectroscopic studies at low temperatures on the LH2 photosynthetic antenna complex from Rhodopseudomonas acidophila. A transfer of this LH2 complex from a bulk-buffer solution into a spin-coated polymer film results in a 189 cm(-1) blue shift of the B850 excitonic absorption band at 5 K. Within the molecular exciton model, the origin of this shift could be disentangled into three parts, namely to an increase of the local site energies, a contraction of the exciton band, and a decrease of the displacement energy.

  5. 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.

  6. Retarded Local Dynamics of Single Fluorescent Probes in Polymeric Glass due to Interaction Strengthening

    Science.gov (United States)

    Zhang, Hao; Yang, Jingfa; Zhao, Jiang

    The effect of strengthening of interaction between single fluorescent probes and polymer matrix to the probes dynamics is investigated using single molecule fluorescence defocus microscopy. By introducing multiple hydroxyl groups to the fluorescent probes, which builds up hydrogen bonds between the probe and polymer matrix, the dynamics is discovered to be retarded. This is evidenced by the lowering of the frequency of the vibrational modes in the power spectra of the rotation trajectories of individual fluorescent probes, and also by the lowering of population of rotating probes. The results show that by strengthening the probe-matrix interaction, the local dynamics detected by the probes is equivalent to that detected by a bigger probe, due to the enhanced friction between the probe and the polymer matrix. the National Basic Research Program of China (2012CB821500).

  7. Study on the interaction between albendazole and eosin Y by fluorescence, resonance Rayleigh scattering and frequency doubling scattering spectra and their analytical applications

    Science.gov (United States)

    Tian, Fengling; Huang, Wei; Yang, Jidong; Li, Qin

    In pH 3.25-3.35 Britton-Robinson (BR) buffer solution, albendazole (ABZ) could react with eosin Y (EY) to form a 1:1 ion-association complex, which not only results in the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS) and frequency doubling scattering (FDS). Furthermore, a new RRS spectrum will appear, and the maximum RRS wavelength was located at about 356 nm. The detection limit for ABZ were 21.51 ng mL-1 for the fluorophotometry, 6.93 ng mL-1 for the RRS method and 12.89 ng mL-1 for the FDS method. Among them, the RRS method had the highest sensitivity. The experimental conditions were optimized and effects of coexisting substances were evaluated. Meanwhile, the influences of coexisting substances were tested. The methods have been successfully applied to the determination of ABZ in capsules and human urine samples. The composition and structure of the ion-association complex and the reaction mechanism were discussed.

  8. Use of details in secondary emission spectra in order to take into account element composition in the radioisotopic, x-ray-fluorescence method

    Energy Technology Data Exchange (ETDEWEB)

    Ivanyukovich, G A; Meier, V A; Nakhabtsev, V S

    1974-01-01

    A study is made of secondary emission spectra applicable to the conditions of determining tin in complex iron ores. Use is made of recorders having an intermediate target of samarium oxide, which assure measurement under geometry of a direct field of vision. It is shown that the integral count rate with a definite selection of the initial condition of discrimination or the count rate in the 32 to 34 keV interval of energies characterizes mainly the composition of the filler. With the purpose of increasing the accuracy and decreasing the effect of equipment factors it is more suitable to estimate the filler composition from the integral count rate. Methods are considered for taking into account the effect of composition of the medium on the measurement results according to the method of spectral ratios by means of a nomogram and analytical expressions. With measurements on models the error of determining the tin content was +- 5 percent in effective atomic number range of 13 to 20, while the error was 50 percent without the introduction of corrections. 10 refs. (tr-auth)

  9. Vibrational Spectral Studies of Gemfibrozil

    Science.gov (United States)

    Benitta, T. Asenath; Balendiran, G. K.; James, C.

    2008-11-01

    The Fourier Transform Raman and infrared spectra of the crystallized drug molecule 5-(2,5-Dimethylphenoxy)-2,2-dimethylpentanoic acid (Gemfibrozil) have been recorded and analyzed. Quantum chemical computational methods have been employed using Gaussian 03 software package based on Hartree Fock method for theoretically modeling the grown molecule. The optimized geometry and vibrational frequencies have been predicted. Observed vibrational modes have been assigned with the aid of normal coordinate analysis.

  10. Investigating the structural origin of trpzip2 temperature dependent unfolding fluorescence line shape based on a Markov state model simulation.

    Science.gov (United States)

    Song, Jian; Gao, Fang; Cui, Raymond Z; Shuang, Feng; Liang, Wanzhen; Huang, Xuhui; Zhuang, Wei

    2012-10-25

    Vibrationally resolved fluorescence spectra of the β-hairpin trpzip2 peptide at two temperatures as well as during a T-jump unfolding process are simulated on the basis of a combination of Markov state models and quantum chemistry schemes. The broad asymmetric spectral line shape feature is reproduced by considering the exciton-phonon couplings. The temperature dependent red shift observed in the experiment has been attributed to the state population changes of specific chromophores. Through further theoretical study, it is found that both the environment's electric field and the chromophores' geometry distortions are responsible for tryptophan fluorescence shift.

  11. Collisional flow of vibrational energy into surrounding vibrational fields within S1 benzene

    International Nuclear Information System (INIS)

    Tang, K.Y.; Parmenter, C.S.

    1983-01-01

    Vapor phase fluorescence spectra are used to determine the absolute rate constants for the collisional transfer of vibrational energy from initial single vibronic levels of S 1 benzene into the surrounding S 1 vibronic field. 11 initial levels are probed with vibrational energies ranging to 2368 cm -1 where the level density is about 10 per cm -1 . CO, isopentane, and S 0 benzene are the collision partners. Benzene rate constants are three to four times gas kinetic for all levels, and electronic energy switching between the initial S 1 molecule and the S 0 collision partner probably makes important contributions. Isopentane efficiencies range from one to two times gas kinetic. Most of the transfer from low S 1 levels occurs with excitation of vibrational energy within isopentane. These V--V contributions decline to only about 10% for the high transfer. CO-induced transfer is by V-T,R processes for all levels. The CO efficiency rises from about 0.1 for low regions to about unity for levels above 1500 cm -1 . The CO efficiencies retain significant sensitivity to initial level identity even in the higher regions. Propensity rules derived from collisional mode-to-mode transfer among lower levels of S 1 benzene are used to calculate the relative CO efficiencies. The calculated efficiencies agree well enough with the data to suggest that it may be meaningful to model vibrational equilibration with the use of propensity rules. The rules suggest that only a small number of levels among the thousands surrounding a high initial level contribute significantly to the total relaxation cross section and that this number is rather independent of the level density

  12. Fluorescence of irradiated hydrocarbons

    International Nuclear Information System (INIS)

    Gulis, I.G.; Evdokimenko, V.M.; Lapkovskij, M.P.; Petrov, P.T.; Gulis, I.M.; Markevich, S.V.

    1977-01-01

    A visible fluorescence has been found out in γ-irradiated aqueous of carbohydrates. Two bands have been distinguished in fluorescence spectra of the irradiated solution of dextran: a short-wave band lambdasub(max)=140 nm (where lambda is a wave length) at lambdasub(β)=380 nm and a long-wave band with lambdasub(max)=540 nm at lambdasub(β)=430 nm. A similar form of the spectrum has been obtained for irradiated solutions of starch, amylopectin, lowmolecular glucose. It has been concluded that a macromolecule of polysaccharides includes fluorescent centres. A relation between fluorescence and α-oxiketon groups formed under irradiation has been pointed out

  13. Development of a fluorescent cryocooler

    International Nuclear Information System (INIS)

    Edwards, B.C.; Buchwald, M.I.; Epstein, R.I.; Gosnell, T.R.; Mungan, C.E.

    1995-01-01

    Recent work at Los Alamos National Laboratory has demonstrated the physical principles for a new type of solid-state cryocooler based on anti-Stokes fluorescence. Design studies indicate that a vibration-free, low-mass ''fluorescent cryocooler'' could operate for years with efficiencies and cooling powers comparable to current commercial systems. This paper presents concepts for a fluorescent cryocooler, design considerations and expected performance

  14. BETA SPECTRA. I. Negatrons spectra

    International Nuclear Information System (INIS)

    Grau Malonda, A.; Garcia-Torano, E.

    1978-01-01

    Using the Fermi theory of beta decay, the beta spectra for 62 negatrons emitters have been computed introducing a correction factor for unique forbidden transitions. These spectra are plotted vs. energy, once normal i sed, and tabulated with the related Fermi functions. The average and median energies are calculated. (Author)

  15. 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...

  16. Competition of bovine serum albumin adsorption and bacterial adhesion onto surface-grafted ODT: in situ study by vibrational SFG and fluorescence confocal microscopy.

    Science.gov (United States)

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

    2012-12-11

    The interaction of hydrophilic and hydrophobic ovococcoid bacteria and bovine serum albumin (BSA) proteins with a well ordered surface of octadecanethiol (ODT) self assembled monolayer (SAM) has been studied in different situations where proteins were either preadsorbed on ODT or adsorbed simultaneously with bacterial adhesion as in life conditions. The two situations lead to very different antimicrobial behavior. Bacterial adhesion on preadsorbed BSA is very limited, while the simultaneous exposure of ODT SAM to proteins and bacteria lead to a markedly weaker antimicrobial effect. The combination of sum frequency generation spectroscopy and fluorescence confocal microscopy experiments allow one to draw conclusions on the factors that govern the ODT SAM or BSA film interaction with bacteria at the molecular level. On the hydrophobic ODT surface, interaction with hydrophobic or hydrophilic biomolecules results in opposite effects on the SAM, namely, a flattening or a raise of the terminal methyl groups of ODT. On an amphiphilic BSA layer, the bacterial adhesion strength is weakened by the negative charges carried by both BSA and bacteria. Surprisingly, preadsorbed BSA that cover part of the bacteria cell walls increase the adhesion strength to the BSA film and reduce hydrophobic interactions with the ODT SAM. Finally, bacterial adhesion on a BSA film is shown to modify the BSA proteins in some way that change their interaction with the ODT SAM. The antimicrobial effect is much stronger in the case of a preadsorbed BSA layer than when BSA and bacteria are in competition to colonize the ODT SAM surface.

  17. Fano Description of Single-Hydrocarbon Fluorescence Excited by a Scanning Tunneling Microscope.

    Science.gov (United States)

    Kröger, Jörg; Doppagne, Benjamin; Scheurer, Fabrice; Schull, Guillaume

    2018-06-13

    The detection of fluorescence with submolecular resolution enables the exploration of spatially varying photon yields and vibronic properties at the single-molecule level. By placing individual polycyclic aromatic hydrocarbon molecules into the plasmon cavity formed by the tip of a scanning tunneling microscope and a NaCl-covered Ag(111) surface, molecular light emission spectra are obtained that unravel vibrational progression. In addition, light spectra unveil a signature of the molecule even when the tunneling current is injected well separated from the molecular emitter. This signature exhibits a distance-dependent Fano profile that reflects the subtle interplay between inelastic tunneling electrons, the molecular exciton and localized plasmons in at-distance as well as on-molecule fluorescence. The presented findings open the path to luminescence of a different class of molecules than investigated before and contribute to the understanding of single-molecule luminescence at surfaces in a unified picture.

  18. Vibrational properties of amorphous semiconductors

    International Nuclear Information System (INIS)

    Schulz, P.A.B.

    1985-01-01

    A model for the lattice dynamics of a-Si 1-X N X is introduced. This model is based on a Born hamiltonian, solved in the Bethe lattice approximation. Starting from the local density of vibrational states, we analize the infrared absoption spectra of this material. (author) [pt

  19. Monothiodibenzoylmethane: Structural and vibrational assignments

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Gorski, Alexander; Posokhov, Yevgen

    2007-01-01

    vibrational spectra were compared with theoretical transitions obtained with B3LYP/cc-pVTZ density functional theory (DFT). The results leave no doubt that the stable ground state configuration of TDBM corresponds to the intramolecularly hydrogen bonded enol form (e-CCC), and that the photoproduct corresponds...

  20. 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.

  1. On the neutron noise diagnostics of pressurized water reactor control rod vibrations II. Stochastic vibrations

    International Nuclear Information System (INIS)

    Pazsit, I.; Glockler, O.

    1984-01-01

    In an earlier publication, using the theory of neutron fluctuations induced by a vibrating control rod, a complete formal solution of rod vibration diagnostics based on neutron noise measurements was given in terms of Fourier-transformed neutron detector time signals. The suggested procedure was checked in numerical simulation tests where only periodic vibrations could be considered. The procedure and its numerical testing are elaborated for stochastic two-dimensional vibrations. A simple stochastic theory of two-dimensional flow-induced vibrations is given; then the diagnostic method is formulated in the stochastic case, that is, in terms of neutron detector auto- and crosspower spectra. A previously suggested approximate rod localization technique is also formulated in the stochastic case. Applicability of the methods is then investigated in numerical simulation tests, using the proposed model of stochastic two-dimensional vibrations when generating neutron detector spectra that simulate measured data

  2. 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

  3. 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...

  4. Raman spectra studies of dipeptides

    International Nuclear Information System (INIS)

    Blanchard, Simone.

    1977-10-01

    This work deals with the homogenous and heterogeneous dipeptides derived from alanine and glycine, in the solid state or in aqueous solutions, in the zwitterions or chlorhydrates form. The Raman spectra comparative study of these various forms of hydrogenated or deuterated compounds allows to specify some of the attributions which are necessary in the conformational study of the like tripeptides. These compounds contain only one peptidic group; therefore there is no possibility of intramolecular hydrogen bond which caracterise vibrations of non bonded peptidic groups and end groups. Infrared spectra of solid dipeptides will be presented and discussed in the near future [fr

  5. Low temperature vibrational spectra, lattice dynamics, and phase transitions in some potassium hexahalometallates: K2[XY6] with X=Sn or Te and Y=Cl or Br

    DEFF Research Database (Denmark)

    Chodos, Steven L.; Berg, Rolf W.

    1979-01-01

    This paper deals with the observation and identification of phonon frequencies resulting from the low temperature phase transitions in K2XY6 crystals. By means of a simple lattice dynamical model, the vibrational Raman and IR data available in the literature and obtained here have been analyzed. ...

  6. Laser induced fluorescence and phosphorescence of matrix isolated glyoxal - Evidence for exciplex formation in the A 1Au and a 3Au states

    Science.gov (United States)

    Van Ijzendoorn, L. J.; Baas, F.; Koernig, S.; Greenberg, J. M.; Allamandola, L. J.

    1986-01-01

    Laser-induced fluorescence and phosphorescence as well as infrared and visible absorption spectra of glyoxal in Ar, N2, and CO matrices are presented and analyzed. Glyoxal in its first excited electronic state is shown to form an exciplex with its nearest neighbors in all three matrices, and transitions normally forbidden dominate the emission spectra. The spectral characteristics of these complexes are similar to those of the Ar-glyoxal complex found in supersonic beam experiments. Due to the matrix cage effect, no vibrational predissociation is observed. The phosphorescence lifetime is determined and an upper limit is given for the fluorescence lifetime. This, in combination with the relative intensities of fluorescence and phosphorescence, can be used to place limits on the quantum yields of the various relaxation processes.

  7. Tool-specific performance of vibration-reducing gloves for attenuating fingers-transmitted vibration

    Science.gov (United States)

    Welcome, Daniel E.; Dong, Ren G.; Xu, Xueyan S.; Warren, Christopher; McDowell, Thomas W.

    2016-01-01

    BACKGROUND Fingers-transmitted vibration can cause vibration-induced white finger. The effectiveness of vibration-reducing (VR) gloves for reducing hand transmitted vibration to the fingers has not been sufficiently examined. OBJECTIVE The objective of this study is to examine tool-specific performance of VR gloves for reducing finger-transmitted vibrations in three orthogonal directions (3D) from powered hand tools. METHODS A transfer function method was used to estimate the tool-specific effectiveness of four typical VR gloves. The transfer functions of the VR glove fingers in three directions were either measured in this study or during a previous study using a 3D laser vibrometer. More than seventy vibration spectra of various tools or machines were used in the estimations. RESULTS When assessed based on frequency-weighted acceleration, the gloves provided little vibration reduction. In some cases, the gloves amplified the vibration by more than 10%, especially the neoprene glove. However, the neoprene glove did the best when the assessment was based on unweighted acceleration. The neoprene glove was able to reduce the vibration by 10% or more of the unweighted vibration for 27 out of the 79 tools. If the dominant vibration of a tool handle or workpiece was in the shear direction relative to the fingers, as observed in the operation of needle scalers, hammer chisels, and bucking bars, the gloves did not reduce the vibration but increased it. CONCLUSIONS This study confirmed that the effectiveness for reducing vibration varied with the gloves and the vibration reduction of each glove depended on tool, vibration direction to the fingers, and finger location. VR gloves, including certified anti-vibration gloves do not provide much vibration reduction when judged based on frequency-weighted acceleration. However, some of the VR gloves can provide more than 10% reduction of the unweighted vibration for some tools or workpieces. Tools and gloves can be matched for

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

    Science.gov (United States)

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

    2016-01-01

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

  9. Rotational structure in molecular infrared spectra

    CERN Document Server

    di Lauro, Carlo

    2013-01-01

    Recent advances in infrared molecular spectroscopy have resulted in sophisticated theoretical and laboratory methods that are difficult to grasp without a solid understanding of the basic principles and underlying theory of vibration-rotation absorption spectroscopy. Rotational Structure in Molecular Infrared Spectra fills the gap between these recent, complex topics and the most elementary methods in the field of rotational structure in the infrared spectra of gaseous molecules. There is an increasing need for people with the skills and knowledge to interpret vibration-rotation spectra in many scientific disciplines, including applications in atmospheric and planetary research. Consequently, the basic principles of vibration-rotation absorption spectroscopy are addressed for contemporary applications. In addition to covering operational quantum mechanical methods, spherical tensor algebra, and group theoretical methods applied to molecular symmetry, attention is also given to phase conventions and their effe...

  10. Spectra and relaxation dynamics of the pseudohalide (PS) vibrational bands for Ru(bpy){sub 2}(PS){sub 2} complexes, PS = CN, NCS and N{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Compton, Ryan; Gerardi, Helen K. [Chemistry Division, Naval Research Laboratory, Washington, DC 20375 (United States); Weidinger, Daniel [SRA International, 4300 Fair Lakes Court, Fairfax, VA 22033 (United States); Brown, Douglas J. [Chemistry Department, US Naval Academy, Annapolis, MD 21402 (United States); Dressick, Walter J. [Center for Bio/Molecular Science and Engineering, Naval Research Laboratory, Washington, DC 20375 (United States); Heilweil, Edwin J. [Radiation and Biomolecular Physics Division, Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Owrutsky, Jeffrey C., E-mail: Jeff.Owrutsky@nrl.navy.mil [Chemistry Division, Naval Research Laboratory, Washington, DC 20375 (United States)

    2013-08-30

    Highlights: ► Static and transient infrared spectroscopy of pseudohalide bipyridine ruthenium complexes. ► Vibrational energy relaxes faster for the azide than the thiocyanate and cyanide analogs. ► Intramolecular vibrational relaxation is prevalent in cis-Ru(bpy){sub 2}(N{sub 3}){sub 2}. - Abstract: Static and transient infrared spectroscopy were used to investigate cis-Ru(bpy){sub 2}(N{sub 3}){sub 2} (bpy = 2,2′-bipyridine), cis-Ru(bpy){sub 2}(NCS){sub 2}, and cis-Ru(bpy){sub 2}(CN){sub 2} in solution. The NC stretching IR band for cis-Ru(bpy){sub 2}(NCS){sub 2} appears at higher frequency (∼2106 cm{sup −1} in DMSO) than for the free NCS{sup −} anion while the IR bands for the azide and cyanide complexes are closer to those of the respective free anions. The vibrational energy relaxation (VER) lifetime for the azide complex is found to be much shorter (∼5 ps) than for either the NCS or CN species (both ∼70 ps in DMSO) and the lifetimes resemble those for each corresponding free anion in solution. However, for cis-Ru(bpy){sub 2}(N{sub 3}){sub 2}, it is determined that the transition frequency depends more on the solvent than the VER lifetime implying that intramolecular vibrational relaxation is predominant over solvent energy-extracting interactions. These results are compared to the behavior of other related metal complexes in solution.

  11. Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

    Science.gov (United States)

    Ahmed, Houssem Eddine; Kamoun, Slaheddine

    2017-09-01

    The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

  12. Vibrating minds

    CERN Multimedia

    2009-01-01

    Ed Witten is one of the leading scientists in the field of string theory, the theory that describes elementary particles as vibrating strings. This week he leaves CERN after having spent a few months here on sabbatical. His wish is that the LHC will unveil supersymmetry.

  13. 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...

  14. Demonstrating Fluorescence with Neon Paper and Plastic

    Science.gov (United States)

    Birriel, Jennifer J.; Roe, Clarissa

    2015-01-01

    Several papers in this journal have dealt with the fluorescence in orange neon plastic, olive oil, and soda. In each case, the fluorescent emission was excited by either green or violet-blue laser light. In this paper, we examine the fluorescent emission spectra of so-called neon colored papers and plastic clipboards available in department and…

  15. Infrared spectra of jennite and tobermorite from first-principles

    Energy Technology Data Exchange (ETDEWEB)

    Vidmer, Alexandre, E-mail: alexandre@vidmer.com; Sclauzero, Gabriele; Pasquarello, Alfredo

    2014-06-01

    The infrared absorption spectra of jennite, tobermorite 14 Å, anomalous tobermorite 11 Å, and normal tobermorite 11 Å are simulated within a density-functional-theory scheme. The atomic coordinates and the cell parameters are optimized resulting in structures which agree with previous studies. The vibrational frequencies and modes are obtained for each mineral. The vibrational density of states is analyzed through extensive projections on silicon tetrahedra, oxygen atoms, OH groups, and water molecules. The coupling with the electric field is achieved through the use of density functional perturbation theory, which yields Born effective charges and dielectric constants. The simulated absorption spectra reproduce well the experimental spectra, thereby allowing for a detailed interpretation of the spectral features in terms of the underlying vibrational modes. In the far-infrared part of the absorption spectra, the interplay between Ca and Si related vibrations leads to differences which are sensitive to the calcium/silicon ratio of the mineral.

  16. On the neutron noise diagnostics of pressurized water reactor control rod vibrations. 1. periodic vibrations

    International Nuclear Information System (INIS)

    Pazsit, I.; Glockler, O.

    1983-01-01

    Based on the theory of neutron noise arising from the vibration of a localized absorber, the possibility of rod vibration diagnostics is investigated. It is found that noise source characteristics, namely rod position and vibration trajectory and spectra, can be unfolded from measured neutron noise signals. For the localization process, the first and more difficult part of the diagnostics, a procedure is suggested whose novelty is that it is applicable in case of arbitrary vibration trajectories. Applicability of the method is investigated in numerical experiments where effects of background noise are also accounted for

  17. Theoretical Prediction of Vibrational Circular Dichroism Spectra of R- Glyceraldehyde, R-Erythrose, and R-Threose. 2. Development of a Procedure to Scale the Force Constant Matrix Expressed in Terms of Internal Coordinates

    Science.gov (United States)

    1993-11-01

    IS PROGRAM NUMBER 1 OF THE COMPLETE VIBRATIONAL PACKAGE. C C BMAT ... WIL.riON B MATRIX ELDEMETS FOR INTERNAL COORDINATES C iVERSIONO JUL 28, 1977) C...MATRIX ISCAN=ISCAN+ 1 IER=O GO TO 30 210 WRITE(6,1120) STOP 1000 FORMAT(20A4/20A4/214) 1010 FORMAT(’l’,20A4,24X.’ BMAT (VERSIONO JUL 28. 1977)’/1X,20A4

  18. Vibration dynamics of single atomic nanocontacts

    International Nuclear Information System (INIS)

    Khater, A; Bourahla, B; Tigrine, R

    2007-01-01

    The motivation for this work is to introduce a model for an atomic nanocontact, whereby its mechanical properties can be analysed via the local spectra. The model system consists of two sets of triple parallel semi-infinite atomic chains joined by a single atom in between. We calculate the vibration spectra and the local densities of vibration states, in the harmonic approximation, for the irreducible set of sites that constitute the nanocontact domain. The nanocontact observables are numerically calculated for different cases of elastic hardening and softening, to investigate how the local dynamics can respond to changes in the microscopic environment on the domain. We have also calculated the phonon scattering and coherent conductance at the nanocontact, derived in a Landauer-Buettiker matrix approach. The analysis of the spectra, of the densities of vibration states, and of the phonon conductance, identifies characteristic features and demonstrates the central role of a core subset of sites in the nanocontact domain

  19. Ab initio Hartree-Fock and density functional theory investigations on the conformational stability, molecular structure and vibrational spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one drug molecule.

    Science.gov (United States)

    Taşal, Erol; Kumalar, Mustafa

    2012-09-01

    In this work, the experimental and theoretical spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule (abbreviated as 5CMOT) are studied. The molecular geometry and vibrational frequencies are calculated in the ground state of molecule using ab initio Hartree-Fock (HF) and Density Function Theory (DFT) methods with 6-311++G(d,p), 6-31G++(d,p), 6-31G(d,p), 6-31G(d) and 6-31G basis sets. Three staggered stable conformers were observed on the torsional potential energy surfaces. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated. The comparison of the theoretical and experimental geometries of the title compound indicated that the X-ray parameters fairly well agree with the theoretically obtained values for the most stable conformer. The theoretical results showed an excellent agreement with the experimental values. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Vibrational and Thermal Properties of Oxyanionic Crystals

    Science.gov (United States)

    Korabel'nikov, D. V.

    2018-03-01

    The vibrational and thermal properties of dolomite and alkali chlorates and perchlorates were studied in the gradient approximation of density functional theory using the method of a linear combination of atomic orbitals (LCAO). Long-wave vibration frequencies, IR and Raman spectra, and mode Gruneisen parameters were calculated. Equation-of-state parameters, thermodynamic potentials, entropy, heat capacity, and thermal expansion coefficient were also determined. The thermal expansion coefficient of dolomite was established to be much lower than for chlorates and perchlorates. The temperature dependence of the heat capacity at T > 200 K was shown to be generally governed by intramolecular vibrations.

  1. Emission spectra of Rb*Hen exciplexes in a cold 4He gas

    International Nuclear Information System (INIS)

    Hirano, K.; Enomoto, K.; Kumakura, M.; Takahashi, Y.; Yabuzaki, T.

    2003-01-01

    We report on the systematic observation of emission spectra of Rb * He n exciplexes (n=1,2,...,6), realized by exciting Rb atoms to the 5 2 P states (Rb * ) in a cold 4 He gas. The observed broad spectral components are assigned to Rb * He n (n=1-6) using theoretical spectra obtained from ab initio potential curves. The dynamics of the exciplex formation is discussed, based on the observed temperature dependence of the spectra. The He gas density dependence of the spectra of Rb * He is understood as a change in the population distribution over the vibrational levels. The present results are compared with our previous work with Cs [K. Enomoto et al., Phys. Rev. A 66, 042505 (2002)], and differences are explained in terms of the difference in the fine-structure splitting. Furthermore, we show the emission spectrum observed after the excitation of Rb in liquid He and conclude that it is the fluorescence from the exciplex Rb * He 6

  2. Fluorescent materials for pH sensing and imaging based on novel 1,4-diketopyrrolo-[3,4-c]pyrrole dyes†Electronic supplementary information (ESI) available: NMR and MS spectra, further sensor characteristics and sensor long-time performance. See DOI: 10.1039/c3tc31130aClick here for additional data file.

    Science.gov (United States)

    Aigner, Daniel; Ungerböck, Birgit; Mayr, Torsten; Saf, Robert; Klimant, Ingo; Borisov, Sergey M

    2013-09-28

    New optical pH-sensors relying on 1,4-diketopyrrolo-[3,4- c ]pyrroles (DPPs) as fluorescent pH-indicators are presented. Different polymer hydrogels are useful as immobilization matrices, achieving excellent sensitivity and good brightness in the resulting sensor. The operational pH can be tuned over a wide range (pH 5-12) by selecting the fine structure of the indicator and the matrix. A ratiometric sensor in the form of nanoparticles is also presented. It is suitable for RGB camera readout, and its practical applicability for fluorescence imaging in microfluidic systems is demonstrated. The indicators are synthesized starting from the commercially available DPP pigments by a straightforward concept employing chlorosulfonation and subsequent reaction with amines. Their sensitivity derives from two distinct mechanisms. At high pH (>9), they exhibit a remarkable alteration of both absorption and fluorescence spectra due to deprotonation of the lactam nitrogen atoms. If a phenolic group is introduced, highly effective fluorescence quenching at near-neutral pH occurs due to photoinduced electron transfer (PET) involving the phenolate form.

  3. Nonsynchronous vibrations observed in a supercritical power transmission shaft

    Science.gov (United States)

    Darlow, M. S.; Zorzi, E. S.

    1979-01-01

    A flexible shaft is prone to a number of vibration phenomena which occur at frequencies other than synchronous with rotational speed. Nonsynchronous vibrations from several sources were observed while running a test rig designed to simulate the operation of a supercritical power transmission shaft. The test rig was run first with very light external damping and then with a higher level of external damping, for comparison. As a result, the effect of external damping on the nonsynchronous vibrations of the test rig was observed. All of these nonsynchronous vibrations were of significant amplitude. Their presence in the vibrations spectra for a supercritical power transmission shaft at various speeds in the operating range indicates that very careful attention to all of the vibration spectra should be made in any supercritical power transmission shafting. This paper presents a review of the analysis performed and a comparison with experimental data. A thorough discussion of the observed nonsynchronous whirl is also provided.

  4. Fluorescence spectroscopy

    DEFF Research Database (Denmark)

    Bagatolli, Luis

    2016-01-01

    Fluorescence spectroscopy is a powerful experimental tool used by scientists from many disciplines. During the last decades there have been important developments on distinct fluorescence methods, particularly those related to the study of biological phenomena. This chapter discusses the foundati......Fluorescence spectroscopy is a powerful experimental tool used by scientists from many disciplines. During the last decades there have been important developments on distinct fluorescence methods, particularly those related to the study of biological phenomena. This chapter discusses...

  5. Resonance Raman and surface-enhanced resonance Raman spectra of LH2 antenna complex from Rhodobacter sphaeroides and Ectothiorhodospira sp. excited in the Qx and Qy transitions.

    Science.gov (United States)

    Chumanov, G; Picorel, R; Ortiz de Zarate, I; Cotton, T M; Seibert, M

    2000-05-01

    Well-resolved vibrational spectra of LH2 complex isolated from two photosynthetic bacteria, Rhodobacter sphaeroides and Ectothiorhodospira sp., were obtained using surface-enhanced resonance Raman scattering (SERRS) exciting into the Qx and the Qy transitions of bacteriochlorophyll a. High-quality SERRS spectra in the Qy region were accessible because the strong fluorescence background was quenched near the roughened Ag surface. A comparison of the spectra obtained with 590 nm and 752 nm excitation in the mid- and low-frequency regions revealed spectral differences between the two LH2 complexes as well as between the LH2 complexes and isolated bacteriochlorophyll a. Because peripheral modes of pigments contribute mainly to the low-frequency spectral region, frequencies and intensities of many vibrational bands in this region are affected by interactions with the protein. The results demonstrate that the microenvironment surrounding the pigments within the two LH2 complexes is somewhat different, despite the fact that the complexes exhibit similar electronic absorption spectra. These differences are most probably due to specific pigment-pigment and pigment-protein interactions within the LH2 complexes, and the approach might be useful for addressing subtle static and dynamic structural variances between pigment-protein complexes from different sources or in complexes altered chemically or genetically.

  6. Hot Ground Vibration Tests

    Data.gov (United States)

    National Aeronautics and Space Administration — Ground vibration tests or modal surveys are routinely conducted to support flutter analysis for subsonic and supersonic vehicles. However, vibration testing...

  7. On the particle-vibration multiplets

    International Nuclear Information System (INIS)

    Khodel, V.A.; Platonov, A.P.; Saperstein, E.E.

    1980-01-01

    The particle-vibration multiplet spectra in the lead region are calculated in the framework of the self-consistent theory of finite Fermi systems. The calculated results are compared with the experimental data and with the results of other authors. (author)

  8. RISK ASSESSMENT BY STRUCTURAL ANALYSIS AND VIBRATION MEASUREMENT EQUIPMENT OPERATING AT OIL FACILITIES

    Directory of Open Access Journals (Sweden)

    Marius STAN

    2013-05-01

    Full Text Available Vibration analysis applications in operation is one of the diagnostic methods ofoperation of the facility. Analysis of these types of failures indicated the existence of specificfeatures prints and related equipment vibration spectra. Modeling and identification of theseparticular aspects in the spectrum of vibration machines help to control the operation of oilfacilities built safely.

  9. RISK ASSESSMENT BY STRUCTURAL ANALYSIS AND VIBRATION MEASUREMENT EQUIPMENT OPERATING AT OIL FACILITIES

    OpenAIRE

    Marius STAN

    2013-01-01

    Vibration analysis applications in operation is one of the diagnostic methods ofoperation of the facility. Analysis of these types of failures indicated the existence of specificfeatures prints and related equipment vibration spectra. Modeling and identification of theseparticular aspects in the spectrum of vibration machines help to control the operation of oilfacilities built safely.

  10. Theory of vibration protection

    CERN Document Server

    Karnovsky, Igor A

    2016-01-01

    This text is an advancement of the theory of vibration protection of mechanical systems with lumped and distributed parameters. The book offers various concepts and methods of solving vibration protection problems, discusses the advantages and disadvantages of different methods, and the fields of their effective applications. Fundamental approaches of vibration protection, which are considered in this book, are the passive, parametric and optimal active vibration protection. The passive vibration protection is based on vibration isolation, vibration damping and dynamic absorbers. Parametric vibration protection theory is based on the Shchipanov-Luzin invariance principle. Optimal active vibration protection theory is based on the Pontryagin principle and the Krein moment method. The book also contains special topics such as suppression of vibrations at the source of their occurrence and the harmful influence of vibrations on humans. Numerous examples, which illustrate the theoretical ideas of each chapter, ar...

  11. 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.

  12. Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

    International Nuclear Information System (INIS)

    Thompson, Michael C.; Weber, J. Mathias; Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2015-01-01

    We report infrared spectra of nitromethane anion, CH 3 NO 2 − , in the region 700–2150 cm −1 , obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states

  13. On the eigenfrequencies of fuel rod vibration in NPPs

    International Nuclear Information System (INIS)

    Lipcsei, S.; Kiss, S.; Por, G.

    1992-05-01

    In neutron fluctuation spectra measured in nuclear reactors, in-core vibrations appear generally as separate frequency peaks. Therefore, neutron fluctuation spectra can be used to analyze these vibrations and to obtain information for diagnostic purposes. Eigenfrequencies of fuel pins were calculated using fourth-order differential equation for vibration. Theoretical results were verified experimentally. It was shown that the series of eigenfrequencies follow a quadratic trend, and in the dependence of eigenfrequencies on constraints the low-order modes are largely influenced. Experimental and calculated results agree fairly well. (R.P.) 13 refs.; 10 figs.; 3 tabs

  14. Vibration monitoring and fault diagnostics of a thermal power plant

    International Nuclear Information System (INIS)

    Hafeez, T.; Ghani, R.; Chohan, G.Y.; Amir, M.

    2003-01-01

    A thermal power plant was monitored from HP-turbine to the generator end. The vibration data at different plant locations was obtained with the help of a data collector/analyzer. The spectra of-all locations generate the symptoms for different problems of moderate and high vibration levels like bent shaft, misalignment in the exciter rotor and three couplings, mechanical looseness on generator and exciter sides. The possible causes of these faults are discussed on the basis of presented vibration spectra in this paper. The faults were later on rectified on the basis of this diagnostics. (author)

  15. Raman Spectra from Pesticides on the Surface of Fruits

    International Nuclear Information System (INIS)

    Zhang, P X; Zhou Xiaofang; Cheng, Andrew Y S; Fang Yan

    2006-01-01

    Raman spectra of several vegetables and fruits were studied by micro-Raman spectrometer (514.5 nm) and Near-infrared Fourier Transform Raman spectrometer (FTRaman). It is shown that at 514.5 nm excitation, most of the spectra are from that of carotene with some very strong fluorescence in some cases. While at 1064 nm wavelength excitation, the spectra from the different samples demonstrate different characteristic Raman spectra without fluorescence. We discuss the spectroscopic difference by the two excitation wavelengths, and the application of Raman spectra for detection of pesticides left on the surface of vegetables and fruits. Raman spectra of fruits and pesticides were successfully recorded, and using the FT-Raman spectra the pesticides left on the surface of the fruits can be detected conveniently

  16. Vibrational and electronic spectroscopic studies of melatonin

    Science.gov (United States)

    Singh, Gurpreet; Abbas, J. M.; Dogra, Sukh Dev; Sachdeva, Ritika; Rai, Bimal; Tripathi, S. K.; Prakash, Satya; Sathe, Vasant; Saini, G. S. S.

    2014-01-01

    We report the infrared absorption and Raman spectra of melatonin recorded with 488 and 632.8 nm excitations in 3600-2700 and 1700-70 cm-1 regions. Further, we optimized molecular structure of the three conformers of melatonin within density functional theory calculations. Vibrational frequencies of all three conformers have also been calculated. Observed vibrational bands have been assigned to different vibrational motions of the molecules on the basis of potential energy distribution calculations and calculated vibrational frequencies. Observed band positions match well with the calculated values after scaling except Nsbnd H stretching mode frequencies. It is found that the observed and calculated frequencies mismatch of Nsbnd H stretching is due to intermolecular interactions between melatonin molecules.

  17. A Miniature Coupled Bistable Vibration Energy Harvester

    International Nuclear Information System (INIS)

    Zhu, D; Arthur, D C; Beeby, S P

    2014-01-01

    This paper reports the design and test of a miniature coupled bistable vibration energy harvester. Operation of a bistable structure largely depends on vibration amplitude rather than frequency, which makes it very promising for wideband vibration energy harvesting applications. A coupled bistable structure consists of a pair of mobile magnets that create two potential wells and thus the bistable phenomenon. It requires lower excitation to trigger bistable operation compared to conventional bistable structures. Based on previous research, this work focused on miniaturisation of the coupled bistable structure for energy harvesting application. The proposed bistable energy harvester is a combination of a Duffing's nonlinear structure and a linear assisting resonator. Experimental results show that the output spectrum of the miniature coupled bistable vibration energy harvester was the superposition of several spectra. It had a higher maximum output power and a much greater bandwidth compared to simply the Duffing's structure without the assisting resonator

  18. Vibration of machine

    International Nuclear Information System (INIS)

    Kwak, Mun Gyu; Na, Sung Su; Baek, Gwang Hyeon; Song, Chul Gi; Han, Sang Bo

    2001-09-01

    This book deals with vibration of machine which gives descriptions of free vibration using SDOF system, forced vibration using SDOF system, vibration of multi-degree of freedom system like introduction and normal form, distribution system such as introduction, free vibration of bar and practice problem, approximate solution like lumped approximations and Raleigh's quotient, engineering by intuition and experience, real problem and experimental method such as technology of signal, fourier transform analysis, frequency analysis and sensor and actuator.

  19. 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.

  20. 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

  1. X-ray fluorescence spectrometry

    International Nuclear Information System (INIS)

    Vries, J.L. de.

    1976-01-01

    The seventh edition of Philips' Review of Literature on x-ray fluorescence spectrometry starts with a list of conference proceedings on the subject, organised by the Philips organisation at regular intervals in various European countries. It is followed by a list of bulletins. The bibliography is subdivided according to spectra, equipment, applications and absorption analysis

  2. Ethane in Planetary and Cometary Atmospheres: Transmittance and Fluorescence Models of the nu7 Band at 3.3 Micrometers

    Science.gov (United States)

    Villanueva, G. L.; Mumma, M. J.; Magee-Sauer, K.

    2011-01-01

    Ethane and other hydrocarbon gases have strong rovibrational transitions in the 3.3 micron spectral region owing to C-H, CH2, and CH3 vibrational modes, making this spectral region prime for searching possible biomarker gases in extraterrestrial atmospheres (e.g., Mars, exoplanets) and organic molecules in comets. However, removing ethane spectral signatures from high-resolution terrestrial transmittance spectra has been imperfect because existing quantum mechanical models have been unable to reproduce the observed spectra with sufficient accuracy. To redress this problem, we constructed a line-by-line model for the n7 band of ethane (C2H6) and applied it to compute telluric transmittances and cometary fluorescence efficiencies. Our model considers accurate spectral parameters, vibration-rotation interactions, and a functional characterization of the torsional hot band. We integrated the new band model into an advanced radiative transfer code for synthesizing the terrestrial atmosphere (LBLRTM), achieving excellent agreement with transmittance data recorded against Mars using three different instruments located in the Northern and Southern hemispheres. The retrieved ethane abundances demonstrate the strong hemispheric asymmetry noted in prior surveys of volatile hydrocarbons. We also retrieved sensitive limits for the abundance of ethane on Mars. The most critical validation of the model was obtained by comparing simulations of C2H6 fluorescent emission with spectra of three hydrocarbon-rich comets: C/2004 Q2 (Machholz), 8P/Tuttle, and C/2007 W1 (Boattini). The new model accurately describes the complex emission morphology of the nu7 band at low rotational temperatures and greatly increases the confidence of the retrieved production rates (and rotational temperatures) with respect to previously available fluorescence models.

  3. Dynamical analysis of highly excited molecular spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kellman, M.E. [Univ. of Oregon, Eugene (United States)

    1993-12-01

    The goal of this program is new methods for analysis of spectra and dynamics of highly excited vibrational states of molecules. In these systems, strong mode coupling and anharmonicity give rise to complicated classical dynamics, and make the simple normal modes analysis unsatisfactory. New methods of spectral analysis, pattern recognition, and assignment are sought using techniques of nonlinear dynamics including bifurcation theory, phase space classification, and quantization of phase space structures. The emphasis is chaotic systems and systems with many degrees of freedom.

  4. [Occupational standing vibration rate and vibrational diseases].

    Science.gov (United States)

    Karnaukh, N G; Vyshchipan, V F; Haumenko, B S

    2003-12-01

    Occupational standing vibration rate is proposed in evaluating a degree of impairment of an organism activity. It will allow more widely to introduce specification of quality and quantity in assessment of the development of vibrational disease. According out-patient and inpatient obtained data we have established criterial values of functional changes in accordance with accumulated occupational standing vibration rate. The nomogram was worked out for defining a risk of the development of vibrational disease in mine workers. This nomogram more objectively can help in diagnostics of the disease.

  5. Fluorescence spectroscopy for neoplasms control

    Science.gov (United States)

    Bratchenko, I. A.; Kristoforova, Yu. A.; Myakinin, O. O.; Artemyev, D. N.; Kozlov, S. V.; Moryatov, A. A.; Zakharov, V. P.

    2016-04-01

    Investigation of malignant skin tumors diagnosis was performed involving two setups for native tissues fluorescence control in visible and near infrared regions. Combined fluorescence analysis for skin malignant melanomas and basal cell carcinomas was performed. Autofluorescence spectra of normal skin and oncological pathologies stimulated by 457 nm and 785 nm lasers were registered for 74 skin tissue samples. Spectra of 10 melanomas and 27 basal cell carcinomas were registered ex vivo. Skin tumors analysis was made on the basis of autofluorescence spectra intensity and curvature for analysis of porphyrins, lipo-pigments, flavins and melanin. Separation of melanomas and basal cell carcinomas was performed on the basis of discriminant analysis. Overall accuracy of basal cell carcinomas and malignant melanomas separation in current study reached 86.5% with 70% sensitivity and 92.6% specificity.

  6. Vibrational spectroscopic study of terbutaline hemisulphate

    Science.gov (United States)

    Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

    2009-05-01

    The Raman spectrum of terbutaline hemisulphate is reported for the first time, and molecular assignments are proposed on the basis of ab initio BLYP DFT calculations with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation; these predictions compare favourably with the observed vibrational spectra. Comparison with previously published infrared data explains several spectral features. The results from this study provide data that can be used for the preparative process monitoring of terbutaline hemisulphate, an important β 2 agonist drug in various dosage forms and its interaction with excipients and other components.

  7. Fluorescing macerals from wood precursors

    Energy Technology Data Exchange (ETDEWEB)

    Stout, S A; Bensley, D F

    1987-01-01

    A preliminary investigation into the origin of wood-derived macerals has established the existence of autofluorescent maceral precursors in the secondary xylem of swamp-inhabiting plant species. The optical character and fluorescent properties of microtomed thin-sections of modern woods from the Florida Everglades and Okefenokee Swamp, Georgia are compared to the character and properties of their peatified equivalents from various Everglades and Okefenokee peat horizons and their lignitic equivalents from the Brandon lignite of Vermont and the Trail Ridge lignitic peat from northern Florida. The inherent fluorescence of woody cell walls is believed to be caused by lignin though other cell wall components may contribute. The fluorescence spectra for several wood and cell types had a ..gamma../sub m//sub a//sub x/ of 452 nm and Q value of 0.00. The color as observed in blue light and the spectral geometry as measured in UV light of peatified and lignitic woody cell walls (potential textinites) may change progressively during early coalification. Cell wall-derived maceral material is shown to maintain its fluorescing properties after being converted to a structureless material, perhaps a corpohuminite or humodetrinite precursor. Fluorescing xylem cell contents, such as condensed tannins or essential oils, can maintain the fluorescent character through early coalification. Xylem cell walls and xylem cell contents are shown to provide fluorescing progenitor materials which would not require subsequent infusion with 'lipid' materials to account for their fluorescence as phytoclast material or as macerals in coal. 35 references.

  8. Beta spectra. II-Positron spectra

    International Nuclear Information System (INIS)

    Grau, A.; Garcia-Torano, E.

    1981-01-01

    Using the Fermi theory of beta decay, the beta spectra for 30 positron emitters have been computed, introducing a correction factor for unique forbidden transitions. The spectra are ploted vs. energy, once normalised, and tabulated with the related Fermi functions. The average and median energies are calculated. (author)

  9. 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.

  10. Contribution of glue layer into epidermis sample fluorescence dynamics

    Science.gov (United States)

    Salomatina, Elena V.; Chernova, Svetlana P.; Pravdin, Alexander B.

    2000-04-01

    In this work, the temporal behavior of autofluorescence of epidermis samples under UV-irradiation has ben studied. The samples were prepared using surface epidermis stripping technique. Fluorescence spectra and kinetic curves of fluorescence intensity have been obtained. It has been concluded that the glue composition used allows the measurement of epidermis fluorescence dynamics with the first 60 min of experiment.

  11. Portable vibration exciter

    Science.gov (United States)

    Beecher, L. C.; Williams, F. T.

    1970-01-01

    Gas-driven vibration exciter produces a sinusoidal excitation function controllable in frequency and in amplitude. It allows direct vibration testing of components under normal loads, removing the possibility of component damage due to high static pressure.

  12. 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.

  13. Vibrations and Eigenvalues

    Indian Academy of Sciences (India)

    We make music by causing strings, membranes, or air columns to vibrate. Engineers design safe structures by control- ling vibrations. I will describe to you a very simple vibrating system and the mathematics needed to analyse it. The ideas were born in the work of Joseph-Louis Lagrange (1736–1813), and I begin by quot-.

  14. Electronic spectra and structures of some biologically important xanthines

    Science.gov (United States)

    Shukla, M. K.; Mishra, P. C.

    1994-08-01

    Electronic absorption and fluorescence spectra of aqueous solutions of xanthine, caffeine, theophylline and theobromine have been studied at different pH. The observed spectra have been interpreted in terms of neutral and ionic forms of the molecules with the help of molecular orbital calculations. At neutral and acidic pH, the spectra can be assigned to the corresponding most stable neutral forms, with the exception that the fluorescence of xanthine at acidic pH appears to originate from the lowest singlet excited state of a cation of the molecule. At alkaline pH, xanthine and theophylline exist mainly as their monoanions. In xanthine and theophylline at alkaline pH, fluorescence originates from the lowest singlet excited state of the corresponding anion. However, in caffeine and theobromine, even at alkaline pH, fluorescence belongs to the neutral species. On the whole, the properties of xanthine are quite different from those of the methyl xanthines.

  15. Polarised IR-microscope spectra of guanidinium hydrogensulphate single crystal.

    Science.gov (United States)

    Drozd, M; Baran, J

    2006-07-01

    Polarised IR-microscope spectra of C(NH(2))(3)*HSO(4) small single crystal samples were measured at room temperature. The spectra are discussed on the basis of oriented gas model approximation and group theory. The stretching nuOH vibration of the hydrogen bond with the Ocdots, three dots, centeredO distance of 2.603A gives characteristic broad AB-type absorption in the IR spectra. The changes of intensity of the AB bands in function of polariser angle are described. Detailed assignments for bands derived from stretching and bending modes of sulphate anions and guanidinium cations were performed. The observed intensities of these bands in polarised infrared spectra were correlated with theoretical calculation of directional cosines of selected transition dipole moments for investigated crystal. The vibrational studies seem to be helpful in understanding of physical and chemical properties of described compound and also in design of new complexes with exactly defined behaviors.

  16. Polarized IR-microscope spectra of guanidinium hydrogenselenate single crystal.

    Science.gov (United States)

    Drozd, M; Baran, J

    2005-10-01

    The polarized IR-microscope spectra of C(NH2)3.HSeO4 small single crystal samples were measured at room temperature. The spectra are discussed with the framework of oriented gas model approximation and group theory. The stretching nuOH vibration of the hydrogen bond with the O...O distance of 2.616 A gives characteristic broad AB-type absorption in the IR spectra. The changes of intensity of the AB bands in function of polarizer angle are described. Detailed assignment for bands derived from stretching and bending modes of selenate anions and guanidinium cations were performed. The observed intensities of these bands in polarized infrared spectra were correlated with theoretical calculation of directional cosines of selected transition dipole moments for investigated crystal. The vibrational studies seem to be helpful in understanding of physical and chemical properties of described compound and also in design of new complexes with exactly defined behaviors.

  17. The Vibrational Spectra of the Boron Halides and Their Molecular ...

    African Journals Online (AJOL)

    NICO

    a cc refers to the cis-cis conformation with respect to the FBNOH chain. b tc refers to the ..... For the intermolecular interactions the values of these quantities ..... Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E.. Peralta, F.

  18. Hydroxyapatite: Vibrational spectra and monoclinic to hexagonal phase transition

    Science.gov (United States)

    Slepko, Alexander; Demkov, Alexander A.

    2015-02-01

    Fundamental studies of biomaterials are necessary to deepen our understanding of their degradation and to develop cure for related illnesses. Biomineral hydroxyapatite Ca10(PO4)6(OH)2 is the main mineral constituent of mammal bone, and its synthetic analogues are used in biomedical applications. The mineral can be found in either hexagonal or monoclinic form. The transformation between these two phases is poorly understood, but knowing its mechanism may be critical to reversing processes in bone related to aging. Using density functional theory, we investigate the mechanisms of the phase transformation and estimate the transition temperature to be 680 K in fair agreement with the experimental temperature of 470 K. We also report the heat capacity of hydroxyapatite and a peculiarity in its phonon dispersion that might allow for non-destructive measurements of the crystal composition with applications in preventive medical screening for bone mineral loss.

  19. Density functional theory study of vibrational spectra, and ...

    Indian Academy of Sciences (India)

    WINTEC

    Spectrophysics Research Laboratory, Pachaiyappa's College, Chennai 600 030 b. Department of ... dynamic properties of dacarbazine were studied using ab initio Hartree–Fock, MP2 and DFT methods. A complete ... of the lymph system and malignant melanoma a type ... the consequent in their qualitative and quantitative.

  20. Vibrational spectra and normal coordinate analysis on structure of ...

    Indian Academy of Sciences (India)

    as high as 840 cm−1. For simple organic chlorine compounds, C–Cl absorptions are in the region 750–700 cm−1 whereas .... Ph.D. Thesis (Bharathidasan University, Tiruchirappalli, Tamil Nadu, India, 1997). [26] S Xavier Jesu Raja, A William ...

  1. Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers

    Science.gov (United States)

    Umreiko, D. S.; Shundalau, M. B.; Zazhogin, A. P.; Komyak, A. I.

    2010-09-01

    Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO2Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO2Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.

  2. Vibrational Raman optical activity of ketose monosaccharides

    Science.gov (United States)

    Bell, Alasdair F.; Hecht, Lutz; Barron, Laurence D.

    1995-07-01

    The vibrational Raman optical activity (ROA) spectra of the four ketose sugars D-fructose, L-sorbose, D-tagatose and D-psicose in aqueous solution, which have been measured in backscattering in the range ≈250-1500 cm -1, are reported. These results are combined with those from a previous ROA study of aldose and pentose sugars in an attempt to establish new vibrational assignments and to verify old ones. The high information content of these spectra provides a new perspective on all the central features of monosaccharide stereochemistry including dominant anomeric configuration, ring conformation, exocyclic CH 2OH group conformation and relative disposition of the hydroxyl groups around the ring.

  3. Fluorescent standards for photodynamic therapy

    Science.gov (United States)

    Belko, N.; Kavalenka, S.; Samtsov, M.

    2016-08-01

    Photodynamic therapy is an evolving technique for treatment of various oncological diseases. This method employs photosensitizers - species that lead to death of tumor cells after the photoactivation. For further development and novel applications of photodynamic therapy new photosensitizers are required. After synthesis of a new photosensitizer it is important to know its concentration in different biological tissues after its administration and distribution. The concentration is frequently measured by the extraction method, which has some disadvantages, e.g. it requires many biological test subjects that are euthanized during the measurement. We propose to measure the photosensitizer concentration in tissue by its fluorescence. For this purpose fluorescent standards were developed. The standards are robust and simple to produce; their fluorescence signal does not change with time. The fluorescence intensity of fluorescent standards seems to depend linearly on the dye concentration. A set of standards thus allow the calibration of a spectrometer. Finally, the photosensitizer concentration can be determined by the fluorescence intensity after comparing the corresponding spectrum with spectra of the set of fluorescent standards. A biological test subject is not euthanized during this kind of experiment. We hope this more humane technique can be used in future instead of the extraction method.

  4. Vibration of hydraulic machinery

    CERN Document Server

    Wu, Yulin; Liu, Shuhong; Dou, Hua-Shu; Qian, Zhongdong

    2013-01-01

    Vibration of Hydraulic Machinery deals with the vibration problem which has significant influence on the safety and reliable operation of hydraulic machinery. It provides new achievements and the latest developments in these areas, even in the basic areas of this subject. The present book covers the fundamentals of mechanical vibration and rotordynamics as well as their main numerical models and analysis methods for the vibration prediction. The mechanical and hydraulic excitations to the vibration are analyzed, and the pressure fluctuations induced by the unsteady turbulent flow is predicted in order to obtain the unsteady loads. This book also discusses the loads, constraint conditions and the elastic and damping characters of the mechanical system, the structure dynamic analysis, the rotor dynamic analysis and the system instability of hydraulic machines, including the illustration of monitoring system for the instability and the vibration in hydraulic units. All the problems are necessary for vibration pr...

  5. Anti-vibration gloves?

    Science.gov (United States)

    Hewitt, Sue; Dong, Ren G; Welcome, Daniel E; McDowell, Thomas W

    2015-03-01

    For exposure to hand-transmitted vibration (HTV), personal protective equipment is sold in the form of anti-vibration (AV) gloves, but it remains unclear how much these gloves actually reduce vibration exposure or prevent the development of hand-arm vibration syndrome in the workplace. This commentary describes some of the issues that surround the classification of AV gloves, the assessment of their effectiveness and their applicability in the workplace. The available information shows that AV gloves are unreliable as devices for controlling HTV exposures. Other means of vibration control, such as using alternative production techniques, low-vibration machinery, routine preventative maintenance regimes, and controlling exposure durations are far more likely to deliver effective vibration reductions and should be implemented. Furthermore, AV gloves may introduce some adverse effects such as increasing grip force and reducing manual dexterity. Therefore, one should balance the benefits of AV gloves and their potential adverse effects if their use is considered. © Crown copyright 2014.

  6. 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.

  7. 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.

  8. Fluorescence spectral properties of stomach tissues with pathology

    Science.gov (United States)

    Giraev, K. M.; Ashurbekov, N. A.; Lahina, M. A.

    2012-05-01

    Steady-state fluorescence and diffuse reflection spectra are measured for in vivo normal and pathological (chronic atrophic and ulcerating defects, malignant neoplasms) stomach mucous lining tissues. The degree of distortion of the fluorescence spectra is estimated taking light scattering and absorption into account. A combination of Gauss and Lorentz functions is used to decompose the fluorescence spectra. Potential groups of fluorophores are determined and indices are introduced to characterize the dynamics of their contributions to the resultant spectra as pathologies develop. Reabsorption is found to quench the fluorescence of structural proteins by as much as a factor of 3, while scattering of the light can increase the fluorescence intensity of flavin and prophyrin groups by as much as a factor of 2.

  9. Shock and vibration technology with applications to electrical systems

    Science.gov (United States)

    Eshleman, R. L.

    1972-01-01

    A survey is presented of shock and vibration technology for electrical systems developed by the aerospace programs. The shock environment is surveyed along with new techniques for modeling, computer simulation, damping, and response analysis. Design techniques based on the use of analog computers, shock spectra, optimization, and nonlinear isolation are discussed. Shock mounting of rotors for performance and survival, and vibration isolation techniques are reviewed.

  10. 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)

  11. Vibrational Investigations of Silver-Doped Hydroxyapatite with Antibacterial Properties

    OpenAIRE

    Ciobanu, Carmen Steluta; Iconaru, Simona Liliana; Le Coustumer, Phillippe; Predoi, Daniela

    2013-01-01

    Silver-doped hydroxyapatite (Ag:HAp) was obtained by coprecipitation method. Transmission electron microscopy (TEM), infrared, and Raman analysis confirmed the development of Ag:HAp with good crystal structure. Transmission electron microscopy analysis showed an uniform ellipsoidal morphology with particles from 5 nm to 15 nm. The main vibrational bands characteristic to HAp were identified. The bands assigned to phosphate vibrational group were highlighted in infrared and Raman spectra. The...

  12. 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)

  13. A Pictorial Visualization of Normal Mode Vibrations of the Fullerene (C[subscript 60]) Molecule in Terms of Vibrations of a Hollow Sphere

    Science.gov (United States)

    Dunn, Janette L.

    2010-01-01

    Understanding the normal mode vibrations of a molecule is important in the analysis of vibrational spectra. However, the complicated 3D motion of large molecules can be difficult to interpret. We show how images of normal modes of the fullerene molecule C[subscript 60] can be made easier to understand by superimposing them on images of the normal…

  14. Fluorescence detection of dental calculus

    Science.gov (United States)

    Gonchukov, S.; Biryukova, T.; Sukhinina, A.; Vdovin, Yu

    2010-11-01

    This work is devoted to the optimization of fluorescence dental calculus diagnostics in optical spectrum. The optimal wavelengths for fluorescence excitation and registration are determined. Two spectral ranges 620 - 645 nm and 340 - 370 nm are the most convenient for supra- and subgingival calculus determination. The simple implementation of differential method free from the necessity of spectrometer using was investigated. Calculus detection reliability in the case of simple implementation is higher than in the case of spectra analysis at optimal wavelengths. The use of modulated excitation light and narrowband detection of informative signal allows us to decrease essentially its diagnostic intensity even in comparison with intensity of the low level laser dental therapy.

  15. Fluorescence spectroscopy for medical and environmental diagnostics

    International Nuclear Information System (INIS)

    Johansson, Jonas.

    1993-09-01

    Fluorescence spectroscopy can be used for diagnostics in medical and environmental applications. The many aspects of fluorescence emission are utilized to enhance the accuracy of the diagnosis. A fluorescence detection system, based on nitrogen laser or dye laser excitation and optical multichannel detection, was constructed, and fluorescence spectra from human malignant tumours of various origins, were recorded. Tumour demarcation was observed using exogenous chromophores, as well as the endogenous tissue fluorescence. In particular, δ-amino levulinic acid was found to provide very good tumour demarcation. A multi-colour imaging system capable of simultaneous recording of four fluorescence images at selected wavelengths, was developed. Examples of processed images, based on the four sub-images, are shown for malignant tumours. In addition, data from photodynamic treatment of human malignant tumours are presented. Autofluorescence spectra from excised pieces of human atherosclerotic aorta and atherosclerotic coronary segment were found to be different from those of non-diseased vessels. Furthermore, fluorescence decay curves from atherosclerotic samples were found to differ from those of non-diseased samples. It is concluded that both spectral and temporal information should be utilized to enhance the demarcation. Methods for obtaining fluorescence data free from interference from blood, with applications to in vivo laser angioplasty of atherosclerosis, are discussed. The optical multichannel system and the multi-colour imaging system were integrated with a remote sensing system, originally used for environmental measurements, to obtain fluorescence spectra as well as fluorescence images of plants at a distance of up to 100 m. The fluorescence data from plants subject to environmental stress or senescent plants were found to differ from those obtained from healthy vegetation. 359 refs

  16. 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.

  17. The VA and VCD spectra of various isotopomers of L-alanine in aqueous solution

    DEFF Research Database (Denmark)

    Abdali, Salim; Jalkanen, Karl J.; Bohr, Henrik

    2002-01-01

    Density functional theory (DFT) at the Becke 3LYP level has been used to calculate the vibrational absorption (VA) and vibrational circular dichroism (VCD) spectra of various deuterated species Of L-alanine. The effect of replacing the methine hydrogen, CH1, the methyl group, CH3, and both...

  18. Prediction of vibration level in tunnel blasting; Tonneru kusshin happa ni yotte reiki sareru shindo no reberu yosoku ho

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, A. [Kumamoto Industries Univ, Kumamoto (Japan); Yamamoto, M. [Asahi Chemical Industry Co. Ltd., Tokyo (Japan); Inaba, C. [Nishimatsu Construction Co. Ltd., Kanagawa (Japan); Kaneko, K. [Hokkaido Univ (Japan)

    1997-08-01

    For avoiding the generation of public hazard due to ground vibration causes by blasting in tunneling, it is important to devise a blasting method for ensuring the level of the ground vibration caused thereby under a limit, and an exact predication of ground vibration before blasting is desirable. In this study, the characteristics of the ground vibration caused by tunnel blasting are analyzed, and a summary of amplitude spectra calculating method is described. A theoretical analysis method for predicting the vibration level is proposed based on spectrum-multiplicative method. Vibration caused by multistage blasting in tunneling is most strong and deemed as important. When observing the process of elastic wave motion caused by multistage blasting being measured, the process can be divided into three element processes in frequency area as vibration source spectrum, transmission attenuation spectrum and frequency response function vibrating test, and, with the multiplication of them, the amplitude spectra at an observation portion can be estimated. 12 refs., 12 figs.

  19. Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations

    Energy Technology Data Exchange (ETDEWEB)

    Wykes, M., E-mail: mikewykes@gmail.com; Parambil, R.; Gierschner, J. [Madrid Institute for Advanced Studies, IMDEA Nanoscience, Calle Faraday 9, Campus Cantoblanco, 28049 Madrid (Spain); Beljonne, D. [Laboratory for Chemistry of Novel Materials, University of Mons, Place du Parc 20, 7000 Mons (Belgium)

    2015-09-21

    Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

  20. The electronic spectra of FeH and TeO2

    International Nuclear Information System (INIS)

    Hullah, D.F.

    1999-01-01

    A thesis submitted for the degree of Doctor of Philosophy at the University of Oxford. Daniel Fearnley Hullah, Jesus College, Trinity Term 1999. This thesis is presented in two parts. The subject of Part One is the recording and analysis of part of the electronic spectrum of the iron monohydride, FeH, at visible wavelengths with Doppler-limited resolution. The subject of Part Two is the recording and analysis of the electronic spectrum of tellurium dioxide, TeO 2 , at near ultra-violet wavelengths under free jet expansion conditions. PART ONE: The fourth sub-bands of the e 6 Π-c 6 Σ + and e 6 Π-a 6 Δ transitions of FeH were recorded using both direct laser induced fluorescence and dispersed laser induced fluorescence. A total of sixteen lines were assigned to the e 6 Π 1/2 -c 6 Σ + -1/2 transition and fourteen lines were assigned to the e 6 Π 1/2 -a 6 Δ 3/2 transition. This allowed the e 6 Π 1/2 spin-orbit component to be characterised for J levels from 1/2 to 7/2 and the a 6 Δ 3/2 spin-orbit component to be characterised for J levels from 3/2 to 9/2. The first sub-band of the e 6 Π-a 6 Δ transition was extended following analysis of the high temperature spectrum of McCormack and O'Connor (recorded in 1976). Dispersed fluorescence spectra of the first four sub-bands of the e 6 Π-a 6 Δ transition were recorded. Following analysis, transitions at ∼ 600 nm were recorded using direct laser induced fluorescence. These were assigned to transitions from the first three spin-orbit components of a new sextet electronic state, b 6 Π (e 6 Π-b 6 Π), one spin orbit component of a new quartet state, C 4 Φ 7/2 , (e 6 Π 5/2 -C 4 Φ 7/2 ), and the previously observed X 4 Δ 7/2 υ = 2 state (e 6 Π 7/2 -X 4 Δ 7/2 υ = 2). PART TWO: The electronic spectrum of TeO 2 was recorded between 345 and 406 nm using a pulsed dye laser. TeO 2 (g) was produced by heating TeO 2(s) to 850 deg. C and entraining the vapour in argon and expanding the gases in a continuous free

  1. Fast Fourier transformation in vibration analysis of physically active systems

    International Nuclear Information System (INIS)

    Hafeez, T.; Amir, M.; Farooq, U.; Day, P.

    2003-01-01

    Vibration of all physical systems may be expressed as the summation of an infinite number of sine and cosine terms known as Fourier series. The basic vibration analysis tool used is the frequency 'spectrum' (a graph of vibration where the amplitude of vibration is plotted against frequency). When a particular rotating component begins to fail, its vibration tends to increase. Spectra graphs are powerful diagnostic tool for detecting components' degradation. Spectra obtained with accelerometers located at the various locations on the components and their analysis in practice from rotating machines enable early detecting of incipient failure. Consequence of unexpected failure can be catastrophic and costly. This study provides basis to relate defective component by its constituent frequencies and then to the known discrete frequency of its 'signature' or 'thumbprint' to predict and verify the sustained dynamic behavior of machine designs harmful effects of forced vibration. The spectra for gearbox of a vane with teeth damaged fault are presented here which signified the importance of FFT analysis as diagnostic tool. This may be helpful to predictive maintenance of the machinery. (author)

  2. Fluorescence microscopy.

    Science.gov (United States)

    Sanderson, Michael J; Smith, Ian; Parker, Ian; Bootman, Martin D

    2014-10-01

    Fluorescence microscopy is a major tool with which to monitor cell physiology. Although the concepts of fluorescence and its optical separation using filters remain similar, microscope design varies with the aim of increasing image contrast and spatial resolution. The basics of wide-field microscopy are outlined to emphasize the selection, advantages, and correct use of laser scanning confocal microscopy, two-photon microscopy, scanning disk confocal microscopy, total internal reflection, and super-resolution microscopy. In addition, the principles of how these microscopes form images are reviewed to appreciate their capabilities, limitations, and constraints for operation. © 2014 Cold Spring Harbor Laboratory Press.

  3. Distributed bearing fault diagnosis based on vibration analysis

    Science.gov (United States)

    Dolenc, Boštjan; Boškoski, Pavle; Juričić, Đani

    2016-01-01

    Distributed bearing faults appear under various circumstances, for example due to electroerosion or the progression of localized faults. Bearings with distributed faults tend to generate more complex vibration patterns than those with localized faults. Despite the frequent occurrence of such faults, their diagnosis has attracted limited attention. This paper examines a method for the diagnosis of distributed bearing faults employing vibration analysis. The vibrational patterns generated are modeled by incorporating the geometrical imperfections of the bearing components. Comparing envelope spectra of vibration signals shows that one can distinguish between localized and distributed faults. Furthermore, a diagnostic procedure for the detection of distributed faults is proposed. This is evaluated on several bearings with naturally born distributed faults, which are compared with fault-free bearings and bearings with localized faults. It is shown experimentally that features extracted from vibrations in fault-free, localized and distributed fault conditions form clearly separable clusters, thus enabling diagnosis.

  4. A Solar-Pumped Fluorescence Model for Line-By-Line Emission Intensities in the B-X, A-X, and X-X Band Systems of 12C14N

    Science.gov (United States)

    Paganini, L.; Mumma, M. J.

    2016-01-01

    We present a new quantitative model for detailed solar-pumped fluorescent emission of the main isotopologue of CN. The derived fluorescence efficiencies permit estimation and interpretation of ro-vibrational infrared line intensities of CN in exospheres exposed to solar (or stellar) radiation. Our g-factors are applicable to astronomical observations of CN extending from infrared to optical wavelengths, and we compare them with previous calculations in the literature. The new model enables extraction of rotational temperature, column abundance, and production rate from astronomical observations of CN in the inner coma of comets. Our model accounts for excitation and de-excitation of rotational levels in the ground vibrational state by collisions, solar excitation to the A(sup 2)Pi(sub I) and B(sup 2)Sum(sup +) electronically excited states followed by cascade to ro-vibrational levels of X(sup 2)Sum(sup +), and direct solar infrared pumping of ro-vibrational levels in the X(sup 2)Sum(sup +) state. The model uses advanced solar spectra acquired at high spectral resolution at the relevant infrared and optical wavelengths and considers the heliocentric radial velocity of the comet (the Swings effect) when assessing the exciting solar flux for a given transition. We present model predictions for the variation of fluorescence rates with rotational temperature and heliocentric radial velocity. Furthermore, we test our fluorescence model by comparing predicted and measured line-by-line intensities for X(sup 2)Sum(sup +) (1-0) in comet C/2014 Q2 (Lovejoy), thereby identifying multiple emission lines observed at IR wavelengths.

  5. 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

  6. 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.)

  7. Study on Properties of Energy Spectra of the Molecular Crystals

    Science.gov (United States)

    Pang, Xiao-Feng; Chen, Xiang-Rong

    The energy-spectra of nonlinear vibration of molecular crystals such as acetanilide have been calculated by using discrete nonlinear Schrödinger equation appropriate to the systems, containing various interactions. The energy levels including higher excited states are basically consistent with experimental values obtained by infrared absorption and Raman scattering in acetanilide. We further give the features of distribution of the energy-spectra for the acetanilide. Using the energy spectra we also explained well experimental results obtained by Careri et al..

  8. Transfer vibration through spine

    OpenAIRE

    Benyovszky, Adam

    2012-01-01

    Transfer Vibration through Spine Abstract In the bachelor project we deal with the topic of Transfer Vibration through Spine. The problem of TVS is trying to be solved by the critical review method. We analyse some diagnostic methods and methods of treatment based on this principle. Close attention is paid to the method of Transfer Vibration through Spine that is being currently solved by The Research Institute of Thermomechanics in The Czech Academy of Sciences in cooperation with Faculty of...

  9. Fluorescence emission behavior of Eu(III) sorbed on calcium silicate hydrates as a secondary mineral formed without drying process

    International Nuclear Information System (INIS)

    Niibori, Yuichi; Narita, Masayuki; Chida, Taiji; Mimura, Hitoshi; Kirishima, Akira

    2014-01-01

    Calcium silicate hydrate (CSH) is a main component of cement-based material required for constructing the geological repository. As in many countries, since the repository in Japan is constructed below water table, we must consider the interaction of radionuclide with cement materials altered around the repository after the backfill. Using fluorescence emission spectra, so far, the authors have investigated the interaction of Eu(III) (as a chemical analog of Am(III)) with CSH gels as a secondary mineral formed without drying process, considering a condition saturated with groundwater. However, in such fluorescence emission behaviors, a deexcitation process of OH vibrators of light water and a quenching effect caused by Eu-Eu energy transfer between Eu atoms incorporated in the CSH gel must be considered. This study examined the fluorescence emission behavior of Eu(III) sorbed on CSH gels, by using La(III) (non-fluorescent ions) as a diluent of Eu(III). Furthermore, CSH samples were synthesized with CaO, SiO 2 , and heavy water (D 2 O) as a solvent in order to avoid the obvious deexcitation process of OH vibrators of light water. In the results, the peak around 618 nm was split into two peaks of 613 nm and 622 nm in the cases of Ca/Si=1.0 and 1.6. Then, the peak of 613 nm decreased with increment of Eu(III)/La(III) ratio. This means that the relative intensity of 613 nm is useful to quantify the amount of Eu(III) incorporated in CSH gel. Besides, the decay behavior of the fluorescence emission did not depend on the Eu/La concentration ratio. That is, such a quenching effect is neglectable. Additionally, the fluorescence emission spectra of Eu(III) showed that the state of Eu(III) depended on Ca/Si ratio of CSH. This suggested that there was several sites in CSH to incorporate Eu(III). When CSH is altered, whole cementitious material in repository must be altered forming cracks and leaching some calcium compositions. Therefore, the adsorptive capacity of CSH might

  10. 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.

  11. Noise and vibration analysis system

    International Nuclear Information System (INIS)

    Johnsen, J.R.; Williams, R.L.

    1985-01-01

    The analysis of noise and vibration data from an operating nuclear plant can provide valuable information that can identify and characterize abnormal conditions. Existing plant monitoring equipment, such as loose parts monitoring systems (LPMS) and neutron flux detectors, may be capable of gathering noise data, but may lack the analytical capability to extract useful meanings hidden in the noise. By analyzing neutron noise signals, the structural motion and integrity of core components can be assessed. Computer analysis makes trending of frequency spectra within a fuel cycle and from one cycle to another a practical means of core internals monitoring. The Babcock and Wilcox Noise and Vibration Analysis System (NVAS) is a powerful, compact system that can automatically perform complex data analysis. The system can acquire, process, and store data, then produce report-quality plots of the important parameter. Software to perform neutron noise analysis and loose parts analysis operates on the same hardware package. Since the system is compact, inexpensive, and easy to operate, it allows utilities to perform more frequency analyses without incurring high costs and provides immediate results

  12. The vibrational dynamics of carbon monoxide in a confined space-CO in zeolites.

    Science.gov (United States)

    Nachtigallová, Dana; Bludský, Ota; Otero Areán, Carlos; Bulánek, Roman; Nachtigall, Petr

    2006-11-14

    Based on theoretical calculations, and a survey of infrared spectra of CO adsorbed on different cation exchanged zeolites, a model is proposed to explain the influence of the zeolite framework on the vibrational behaviour of CO confined into small void spaces (zeolite channels and cavities). The concepts developed should help to understand a number of details relevant to both, precise interpretation of IR spectra and a better understanding of the vibrational dynamics of small molecules in a confined space.

  13. Spectra of Graphs

    NARCIS (Netherlands)

    Brouwer, A.E.; Haemers, W.H.

    2012-01-01

    This book gives an elementary treatment of the basic material about graph spectra, both for ordinary, and Laplace and Seidel spectra. The text progresses systematically, by covering standard topics before presenting some new material on trees, strongly regular graphs, two-graphs, association

  14. Spectra of alkali atoms

    International Nuclear Information System (INIS)

    Santoso, Budi; Arumbinang, Haryono.

    1981-01-01

    Emission spectra of alkali atoms has been determined by using spectrometer at the ultraviolet to infra red waves range. The spectra emission can be obtained by absorption spectrophotometric analysis. Comparative evaluations between experimental data and data handbook obtained by spark method were also presented. (author tr.)

  15. Using Molecular Modeling in Teaching Group Theory Analysis of the Infrared Spectra of Organometallic Compounds

    Science.gov (United States)

    Wang, Lihua

    2012-01-01

    A new method is introduced for teaching group theory analysis of the infrared spectra of organometallic compounds using molecular modeling. The main focus of this method is to enhance student understanding of the symmetry properties of vibrational modes and of the group theory analysis of infrared (IR) spectra by using visual aids provided by…

  16. Mechanical vibration and shock analysis, sinusoidal vibration

    CERN Document Server

    Lalanne, Christian

    2014-01-01

    Everything engineers need to know about mechanical vibration and shock...in one authoritative reference work! This fully updated and revised 3rd edition addresses the entire field of mechanical vibration and shock as one of the most important types of load and stress applied to structures, machines and components in the real world. Examples include everything from the regular and predictable loads applied to turbines, motors or helicopters by the spinning of their constituent parts to the ability of buildings to withstand damage from wind loads or explosions, and the need for cars to m

  17. Hydroelastic Vibrations of Ships

    DEFF Research Database (Denmark)

    Jensen, Jørgen Juncher; Folsø, Rasmus

    2002-01-01

    A formula for the necessary hull girder bending stiffness required to avoid serious springing vibrations is derived. The expression takes into account the zero crossing period of the waves, the ship speed and main dimensions. For whipping vibrations the probability of exceedance for the combined...

  18. 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

  19. Gearbox vibration diagnostic analyzer

    Science.gov (United States)

    1992-01-01

    This report describes the Gearbox Vibration Diagnostic Analyzer installed in the NASA Lewis Research Center's 500 HP Helicopter Transmission Test Stand to monitor gearbox testing. The vibration of the gearbox is analyzed using diagnostic algorithms to calculate a parameter indicating damaged components.

  20. Handbook Of Noise And Vibration

    International Nuclear Information System (INIS)

    1995-12-01

    This book is about noise and vibration. The first chapter has explanations of noise such as basic of sound, influence of noise, assessment of noise, measurement of prevention of noise and technology, case of noise measurement and soundproof. The second chapter describes vibration with outline, theory of vibration, interpretation of vibration, measurement for reduction of vibration, case of design of protection against vibration. It deals with related regulation and method of measurement.

  1. Vibration insensitive interferometry

    Science.gov (United States)

    Millerd, James; Brock, Neal; Hayes, John; Kimbrough, Brad; North-Morris, Michael; Wyant, James C.

    2017-11-01

    The largest limitation of phase-shifting interferometry for optical testing is the sensitivity to the environment, both vibration and air turbulence. An interferometer using temporal phase-shifting is very sensitive to vibration because the various phase shifted frames of interferometric data are taken at different times and vibration causes the phase shifts between the data frames to be different from what is desired. Vibration effects can be reduced by taking all the phase shifted frames simultaneously and turbulence effects can be reduced by averaging many measurements. There are several techniques for simultaneously obtaining several phase-shifted interferograms and this paper will discuss two such techniques: 1) Simultaneous phase-shifting interferometry on a single detector array (PhaseCam) and 2) Micropolarizer phase-shifting array. The application of these techniques for the testing of large optical components, measurement of vibrational modes, the phasing of segmented optical components, and the measurement of deformations of large diffuse structures is described.

  2. Vibrations of rotating machinery

    CERN Document Server

    Matsushita, Osami; Kanki, Hiroshi; Kobayashi, Masao; Keogh, Patrick

    2017-01-01

    This book opens with an explanation of the vibrations of a single degree-of-freedom (dof) system for all beginners. Subsequently, vibration analysis of multi-dof systems is explained by modal analysis. Mode synthesis modeling is then introduced for system reduction, which aids understanding in a simplified manner of how complicated rotors behave. Rotor balancing techniques are offered for rigid and flexible rotors through several examples. Consideration of gyroscopic influences on the rotordynamics is then provided and vibration evaluation of a rotor-bearing system is emphasized in terms of forward and backward whirl rotor motions through eigenvalue (natural frequency and damping ratio) analysis. In addition to these rotordynamics concerning rotating shaft vibration measured in a stationary reference frame, blade vibrations are analyzed with Coriolis forces expressed in a rotating reference frame. Other phenomena that may be assessed in stationary and rotating reference frames include stability characteristic...

  3. TRANES analysis of the fluorescence of nile red in organized ...

    Indian Academy of Sciences (India)

    Unknown

    Department of Chemical Sciences, Tata Institute of Fundamental Research, ... Construction of time-resolved emission spectra (TRES) is a useful method 1. If the ..... 1992–2000 Topics in fluorescence spectroscopy (New York: Plenum) vol. 1–5 ...

  4. A coumarin-based colorimetric fluorescent probe for hydrogen sulfide

    Indian Academy of Sciences (India)

    with nitric oxide (NO) and carbon monoxide (CO), which mediate ... esterification, no emission of the fluorophore would be found due to ... Fluorescence emission spectra were obtained ... of excessive organic solvent might restrict the practical.

  5. The Shock and Vibration Bulletin. Part 3. Skylab, Vibration Testing and Analysis

    Science.gov (United States)

    1973-06-01

    SPECTRA D, 0. Smallwood , Sandia Laboratories, Albuquerque, New Mexico and A. F. Witte, Kaman Sciences, Colorado Springs, Colorado A TRANSIENT VIBRATION TEST...TECHNIQUE USING LEAST FAVORABLE RESPONSES D. 0. Smallwood , Sandia Laboratories, Albuquerque, New Mexico PAPERS APPEARING IN PART 2 Structural...form of the time history pdf is REFERENCES determined to be independent of changes in flight condition and sensor location, the 1. Norman Johnson and

  6. Laser-Induced Fluorescence (LIF) from plant foliage

    Science.gov (United States)

    Chappelle, Emmett W.; Williams, Darrel L.

    1987-01-01

    The fluorescence spectra and fluorescence induction kinetics of green plants excited at 337 nm by a laser were studied. They correlate with plant type, as well as with changes in the physiology of the plant as the result of stress. The plant types studied include herbaceous dicots, monocots, hardwoods, conifers, and algae. These plant types could be identified on the basis of differences in either the number of fluorescent bands or the relative intensity of the bands. Differences in fluorescent spectra which could be related to vigor status are observed in conifers located in an area of high atmospheric deposition. Changes in the fluorescence spectra and induction kinetics are also seen in plants grown under conditions of nutrient deficiency and drought stress.

  7. ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

    Science.gov (United States)

    Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

    2013-11-07

    The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

  8. 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.

  9. Vibrational Analysis of (SCN)2 and the Transient (SCN)2

    DEFF Research Database (Denmark)

    Jensen, N. H.; Wilbrandt, Robert Walter; Pagsberg, Palle Bjørn

    1979-01-01

    The vibrational spectra of thiocyanogen and the transient radical anion (SCN)2− are interpreted in detail through molecular orbital and normal coordinate calculations. The results support the assignment of (SCN)2− to the anion of thiocyanogen and indicate a substantial weakening of the S–S and C......≡N bonds in going from the parent molecule to its radical anion....

  10. Overhead traveling crane vibration research using experimental wireless measuring system

    Directory of Open Access Journals (Sweden)

    Tomasz HANISZEWSKI

    2013-01-01

    Full Text Available The paper contains an operations and constructions description of theexperimental wireless measuring system for measuring accelerations in bridge cranes,based on PHIDGET 1056 sensors. Developed experimental research and measuringmethodology allows the use of the proposed wireless system on other cranesconstructions. The paper also shows examples of the results of vibration measurementsand FFT spectra, obtained on the basis of accelerations measurements.

  11. First-principles analysis of the Raman spectrum of vitreous silica: comparison with the vibrational density of states

    International Nuclear Information System (INIS)

    Umari, P; Pasquarello, Alfredo

    2003-01-01

    The HH and HV Raman spectra of vitreous silica are calculated from first principles for a model structure consisting of a disordered network of corner-sharing tetrahedra, for which the vibrational properties were obtained previously. We analyse the contribution of specific atomic motions to the Raman spectra and perform a detailed comparison with respect to the vibrational density of states. We find that the HV spectrum closely resembles the vibrational density of states. By comparison, the HH spectrum shows significant differences and arises almost exclusively from oxygen vibrations

  12. First-principles analysis of the Raman spectrum of vitreous silica: comparison with the vibrational density of states

    Energy Technology Data Exchange (ETDEWEB)

    Umari, P; Pasquarello, Alfredo [Institut de Theorie des Phenomenes Physiques (ITP), Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland); Institut Romand de Recherche Numerique en Physique des Materiaux (IRRMA), CH-1015 Lausanne (Switzerland)

    2003-04-30

    The HH and HV Raman spectra of vitreous silica are calculated from first principles for a model structure consisting of a disordered network of corner-sharing tetrahedra, for which the vibrational properties were obtained previously. We analyse the contribution of specific atomic motions to the Raman spectra and perform a detailed comparison with respect to the vibrational density of states. We find that the HV spectrum closely resembles the vibrational density of states. By comparison, the HH spectrum shows significant differences and arises almost exclusively from oxygen vibrations.

  13. New N2(C 3Πu, v) collision quenching and vibrational relaxation rate constants: 2. PG emission diagnostics of high-pressure discharges

    International Nuclear Information System (INIS)

    Dilecce, G; Ambrico, P F; De Benedictis, S

    2007-01-01

    The present paper deals with the determination of discharge parameters using N 2 (C 3 Π u , v) populations deduced from 2.PG emission spectra, focusing on the influence of N 2 (C 3 Π u , v) collision rate coefficients on these determinations. In particular it is shown that the new set of quenching and vibrational relaxation rate coefficients of N 2 (C 3 Π u , v 0-4) vibronic levels recently measured by optical-optical double resonance laser induced fluorescence (LIF) have a large effect on discharge parameter determination in high-pressure discharges. In the present paper we explore this effect, evidencing the differences with respect to the old data set case, in both simulated and real cases of N 2 (C 3 Π u , v) vibrational distributions measured at high pressure in a dielectric barrier discharge. Finally we point out the improved potentiality of 2.PG spectroscopy as a diagnostic technique: with the new rate coefficients, and measurement of the N 2 (C 3 Π u , v) distribution up to at least v = 3, it is possible to have a quasi-independent evaluation of the electron temperature and of the first level vibrational temperature of the N 2 ground state

  14. Optimal Fluorescence Waveband Determination for Detecting Defective Cherry Tomatoes Using a Fluorescence Excitation-Emission Matrix

    Directory of Open Access Journals (Sweden)

    In-Suck Baek

    2014-11-01

    Full Text Available A multi-spectral fluorescence imaging technique was used to detect defective cherry tomatoes. The fluorescence excitation and emission matrix was used to measure for defects, sound surface and stem areas to determine the optimal fluorescence excitation and emission wavelengths for discrimination. Two-way ANOVA revealed the optimal excitation wavelength for detecting defect areas was 410 nm. Principal component analysis (PCA was applied to the fluorescence emission spectra of all regions at 410 nm excitation to determine the emission wavelengths for defect detection. The major emission wavelengths were 688 nm and 506 nm for the detection. Fluorescence images combined with the determined emission wavebands demonstrated the feasibility of detecting defective cherry tomatoes with >98% accuracy. Multi-spectral fluorescence imaging has potential utility in non-destructive quality sorting of cherry tomatoes.

  15. Vibration-reducing gloves: transmissibility at the palm of the hand in three orthogonal directions.

    Science.gov (United States)

    McDowell, Thomas W; Dong, Ren G; Welcome, Daniel E; Xu, Xueyan S; Warren, Christopher

    2013-01-01

    Vibration-reducing (VR) gloves are commonly used as a means to help control exposures to hand-transmitted vibrations generated by powered hand tools. The objective of this study was to characterise the vibration transmissibility spectra and frequency-weighted vibration transmissibility of VR gloves at the palm of the hand in three orthogonal directions. Seven adult males participated in the evaluation of seven glove models using a three-dimensional hand-arm vibration test system. Three levels of hand coupling force were applied in the experiment. This study found that, in general, VR gloves are most effective at reducing vibrations transmitted to the palm along the forearm direction. Gloves that are found to be superior at reducing vibrations in the forearm direction may not be more effective in the other directions when compared with other VR gloves. This casts doubts on the validity of the standardised glove screening test. Practitioner Summary: This study used human subjects to measure three-dimensional vibration transmissibility of vibration-reducing gloves at the palm and identified their vibration attenuation characteristics. This study found the gloves to be most effective at reducing vibrations along the forearm direction. These gloves did not effectively attenuate vibration along the handle axial direction.

  16. Silicon micromachined vibrating gyroscopes

    Science.gov (United States)

    Voss, Ralf

    1997-09-01

    This work gives an overview of silicon micromachined vibrating gyroscopes. Market perspectives and fields of application are pointed out. The advantage of using silicon micromachining is discussed and estimations of the desired performance, especially for automobiles are given. The general principle of vibrating gyroscopes is explained. Vibrating silicon gyroscopes can be divided into seven classes. for each class the characteristic principle is presented and examples are given. Finally a specific sensor, based on a tuning fork for automotive applications with a sensitivity of 250(mu) V/degrees is described in detail.

  17. System Detects Vibrational Instabilities

    Science.gov (United States)

    Bozeman, Richard J., Jr.

    1990-01-01

    Sustained vibrations at two critical frequencies trigger diagnostic response or shutdown. Vibration-analyzing electronic system detects instabilities of combustion in rocket engine. Controls pulse-mode firing of engine and identifies vibrations above threshold amplitude at 5.9 and/or 12kHz. Adapted to other detection and/or control schemes involving simultaneous real-time detection of signals above or below preset amplitudes at two or more specified frequencies. Potential applications include rotating machinery and encoders and decoders in security systems.

  18. 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.

  19. Single oligomer spectra probe chromophore nanoenvironments of tetrameric fluorescent proteins

    NARCIS (Netherlands)

    Blum, Christian; Meixner, Alfred J; Subramaniam, Vinod

    2006-01-01

    When analyzing the emission of a large number of individual chromophores embedded in a matrix, the spread of the observed parameters is a characteristic property for the particular chromophore-matrix system. To quantitatively assess the influence of the matrix on the single molecule emission

  20. Single Oligomer Spectra Probe Chromophore Nanoenvironments of Tetrameric Fluorescent Proteins

    NARCIS (Netherlands)

    Blum, Christian; Meixner, Alfred J.; Subramaniam, Vinod

    2006-01-01

    When analyzing the emission of a large number of individual chromophores embedded in a matrix, the spread of the observed parameters is a characteristic property for the particular chromophore−matrix system. To quantitatively assess the influence of the matrix on the single molecule emission