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

Full-dimensional characterization of photoelectron spectra of HOCO− and DOCO− and tunneling facilitated decay of HOCO prepared by anion photodetachment

International Nuclear Information System (INIS)

Wang, Jun; Li, Jun; Guo, Hua; Ma, Jianyi

2014-01-01

The photodetachment of both the HOCO − and DOCO − anions is investigated using full-dimensional quantum wave packets on new ab initio based global potential energy surfaces for both the neutral and anionic species. The calculated electron affinities and neutral fundamental vibrational frequencies of both isotopomers are in good agreement with available experimental data. The measured photoelectron spectra are also accurately reproduced, further validating the accuracy of the potential energy surfaces. In addition, strong mode specificity is found in the lifetimes of the HOCO vibrational features and the tunneling facilitated predissociation rates to H + CO 2 are rationalized using the recently proposed sudden vector projection model

Role of ion-pair states in the predissociation dynamics of Rydberg states of molecular iodine.

Science.gov (United States)

von Vangerow, J; Bogomolov, A S; Dozmorov, N V; Schomas, D; Stienkemeier, F; Baklanov, A V; Mudrich, M

2016-07-28

Using femtosecond pump-probe ion imaging spectroscopy, we establish the key role of I(+) + I(-) ion-pair (IP) states in the predissociation dynamics of molecular iodine I2 excited to Rydberg states. Two-photon excitation of Rydberg states lying above the lowest IP state dissociation threshold (1st tier) is found to be followed by direct parallel transitions into IP states of the 1st tier asymptotically correlating to a pair of I ions in their lowest states I(+)((3)P2) + I(-)((1)S0), of the 2nd tier correlating to I(+)((3)P0) + I(-)((1)S0), and of the 3rd tier correlating to I(+)((1)D2) + I(-)((1)S0). Predissociation via the 1st tier proceeds presumably with a delay of 1.6-1.7 ps which is close to the vibrational period in the 3rd tier state (3rd tier-mediated process). The 2nd tier IP state is concluded to be the main precursor for predissociation via lower lying Rydberg states proceeding with a characteristic time of 7-8 ps and giving rise to Rydberg atoms I(5s(2)5p(4)6s(1)). The channel generating I((2)P3/2) + I((2)P1/2) atoms with total kinetic energy corresponding to one-photon excitation is found to proceed via a pump - dump mechanism with dramatic change of angular anisotropy of this channel as compared with earlier nanosecond experiments.

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

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

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.

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

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

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

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.

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)

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)].

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.

Predissociation measurements of bond dissociation energies: VC, VN, and VS

Energy Technology Data Exchange (ETDEWEB)

Johnson, Eric L.; Davis, Quincy C.; Morse, Michael D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 (United States)

2016-06-21

The abrupt onset of predissociation in the congested electronic spectra of jet-cooled VC, VN, and VS has been observed using resonant two-photon ionization spectroscopy. It is argued that because of the high density of electronic states in these molecules, the predissociation threshold occurs at the thermochemical threshold for the production of separated atoms in their ground electronic states. As a result, the measured threshold represents the bond dissociation energy. Using this method, bond dissociation energies of D{sub 0}(V C) = 4.1086(25) eV, D{sub 0}(V N) = 4.9968(20) eV, and D{sub 0}(V S) = 4.5353(25) eV are obtained. From these values, enthalpies of formation are derived as Δ{sub f,0K}H°(V C(g)) = 827.0 ± 8 kJ mol{sup −1}, Δ{sub f,0K}H°(V N(g)) = 500.9 ± 8 kJ mol{sup −1}, and Δ{sub f,0K}H°(V S(g)) = 349.3 ± 8 kJ mol{sup −1}. Using a thermochemical cycle and the well-known ionization energies of V, VC, and VN, our results also provide D{sub 0}(V{sup +}–C) = 3.7242(25) eV and D{sub 0}(V{sup +}–N) = 4.6871(20) eV. These values are compared to previous measurements and to computational results. The precision of these bond dissociation energies makes them good candidates for testing computational chemistry methods, particularly those that employ density functional theory.

Observation of the Stark effect in υ+ = 0 Rydberg states of NO: a comparison between predissociating and bound states

International Nuclear Information System (INIS)

Jones, N J A; Minns, R S; Patel, R; Fielding, H H

2008-01-01

The Stark spectra of Rydberg states of NO below the υ + = 0 ionization limit, with principal quantum numbers n = 25-30, have been investigated in the presence of dc electric fields in the range 0-150 V cm -1 . The Stark states were accessed by two-colour, double-resonance excitation via the υ' = 0, N' = 0 rovibrational state of the A 2 Σ + state. The N( 2 D) atoms produced by predissociation were measured by (2 + 1) resonance-enhanced multiphoton ionization, and compared with pulsed-field ionization spectra of the bound Rydberg state population (Patel et al 2007 J. Phys. B: At. Mol. Opt. Phys. 40 1369)

Resonances in photoabsorption: Predissociation line shapes in the 3pπD1Π+u ← Χ1Σg+ system in H2

International Nuclear Information System (INIS)

Mezei, J. Zs.; Schneider, I. F.; Glass-Maujean, M.; Jungen, Ch.

2014-01-01

The predissociation of the 3pπD 1 Π u + ,v≥3,N=1, N = 2, and N = 3 levels of diatomic hydrogen is calculated by ab initio multichannel quantum defect theory combined with a R-matrix type approach that accounts for interfering predissociation and autoionization. The theory yields absorption line widths and shapes that are in good agreement with those observed in the high-resolution synchrotron vacuum-ultraviolet absorption spectra obtained by Dickenson et al. [J. Chem. Phys. 133, 144317 (2010)] at the DESIRS beamline of the SOLEIL synchrotron. The theory predicts further that many of the D state resonances with v ⩾ 6 exhibit a complex fine structure which cannot be modeled by the Fano profile formula and which has not yet been observed experimentally

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 ...

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)

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

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

VUV spectroscopic study of the ? state of H2

Science.gov (United States)

Dickenson, G. D.; Ubachs, W.

2014-04-01

Spectral lines, probing rotational quantum states J‧ = 0, 1, 2 of the inner well vibrations (υ‧ ≤ 8) in the ? state of molecular hydrogen, were recorded in high resolution using a vacuum ultraviolet Fourier transform absorption spectrometer in the wavelength range 73-86 nm. Accurate line positions and predissociation widths are determined from a fit to the absorption spectra. Improved values for the line positions are obtained, while the predissociation widths agree well with previous investigations.

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.

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

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.

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

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.

NH4(+) Resides Inside the Water 20-mer Cage As Opposed to H3O(+), Which Resides on the Surface: A First Principles Molecular Dynamics Simulation Study.

Science.gov (United States)

Willow, Soohaeng Yoo; Singh, N Jiten; Kim, Kwang S

2011-11-08

Experimental vibrational predissociation spectra of the magic NH4(+)(H2O)20 clusters are close to those of the magic H3O(+)(H2O)20 clusters. It has been assumed that the geometric features of NH4(+)(H2O)20 clusters might be close to those of H3O(+)(H2O)20 clusters, in which H3O(+) resides on the surface. Car-Parrinello molecular dynamics simulations in conjunction with density functional theory calculations are performed to generate the infrared spectra of the magic NH4(+)(H2O)20 clusters. In comparison with the experimental vibrational predissociation spectra of NH4(+)(H2O)20, we find that NH4(+) is inside the cage structure of NH4(+)(H2O)20 as opposed to on the surface structure. This shows a clear distinction between the structures of NH4(+)(H2O)20 and H3O(+)(H2O)20 as well as between the hydration phenomena of NH4(+) and H3O(+).

Raman spectrum of predissociating H/sub 2/S

International Nuclear Information System (INIS)

Kleinermanns, K.; Suntz, R.; Schneider, R.

1986-01-01

Emission spectroscopy of photodissociating molecules provides interesting insights into the short-time dynamics of bond raptures. The authors report here a resolved H/sub 2/S photoemission spectrum after excitation at 193 nm, although its electronic spectrum in this wavelength region is diffuse. The electronic spectrum of H/sub 2/S between 250 and 170 nm is nearly continuous probably due to predissociation

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 ...

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.

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.

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.

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

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

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

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 ...

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)

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.

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.

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.

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

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.

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).

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

Ir-Driven Dynamics of the 3-AMINOPHENOL-AMMONIA Complex

Science.gov (United States)

Heid, Cornelia G.; Merrill, W. G.; Case, Amanda; Crim, Fleming

2014-06-01

We report on gas-phase experiments investigating the predissociation and possible IR-driven isomerization of the 3-aminophenol-ammonia complex (3-AP-NH3). A molecular beam of 3-AP-NH3 is vibrationally excited with pulsed IR light, initiating an intramolecular vibrational redistribution and subsequent dissociation. The 3-AP fragment is then probed state-selectively via multiphoton ionization (REMPI) and time-of-flight mass spectrometry. Of particular interest is an IR-driven feature which we associate tentatively with a trans-cis isomerization process. We see clear correlation between the excitation of specific vibrational modes (namely the NH3 symmetric and OH stretches) and the presence of this feature, as evidenced by IR-action and IR-depletion spectra. The feature persists atop a broader signal which we assign to the predissociation of the complex and whose cutoff in REMPI-action experiments provides an upper bound on the dissociation energy for 3-AP-NH3.

Etude du mecanisme de predissociation de l'ion moleculaire de protoxyde d'azote par la mesure de l'energie cinetique des fragments de l'oxyde nitrique et de l'oxygene

Science.gov (United States)

Delisle, Claude

La reaction N2 + O+ ↔ NO + + N, laquelle joue un role important dans la physique de la haute atmosphere, a ete le sujet de plusieurs etudes. Bien que cette reaction ait ete l'objet d'une quantite importante de travaux, ces derniers ne permettent toutefois pas de comprendre entierement le mecanisme d'un point de vue quantique, particulierement les niveaux d'energie excites des fragments qui permettent cette reaction. Puisque cette reaction n'est pas tres facile a reproduire en laboratoire, nous avons utilise la spectroscopie laser sur faisceaux d'ions rapides afin d'explorer les limites de dissociation de l'ion moleculaire intermediaire de cette reaction, a savoir l'ion N2O+. Le faisceau d'ions N2O+ rapides, apres excitation de l'ion moleculaire vers un niveau predissocie de l'etat A2Sigma+, se dissocie pour produire les fragments ioniques O+ et NO+. Par la mesure de la variation du nombre de fragments ioniques en fonction de l'energie cinetique des ions N2O+, nous avons enregistre les spectres de predissociation de l'ion N2O+. Lorsque c'etait possible, nous avons procede a l'analyse de ces spectres de dissociation afin d'en tirer les constantes moleculaires. Pour certaines des transitions rotationnelles intenses, nous avons mesure l'energie cinetique acquise par les fragments lors de la predissociation de l'ion N 2O+. Afin d'analyser les distributions en energie cinetique, nous avons developpe une simulation de l'experience en considerant, entre autres choses, la position des niveaux de vibration et de rotation des fragments diatomiques de chacune des limites de dissociation de N2O+. Les resultats de l'analyse sont exprimes en termes de population des niveaux de vibration des fragments diatomiques pour une distribution donnee de la population des niveaux de rotation des fragments. Les resultats ainsi obtenus, montrent que les fragments diatomiques sont produits dans des niveaux de vibration fortement excites. De tels niveaux d'excitation ne correspondent pas aux

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

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.

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.

Photofragment angular momentum distribution beyond the axial recoil approximation: Predissociation

International Nuclear Information System (INIS)

Kuznetsov, Vladislav V.; Vasyutinskii, Oleg S.

2007-01-01

We present the quantum mechanical expressions for the angular momentum distribution of the photofragments produced in slow predissociation. The paper is based on our recent theoretical treatment [J. Chem. Phys. 123, 034307 (2005)] of the recoil angle dependence of the photofragment multipole moments which explicitly treat the role of molecular axis rotation on the electronic angular momentum polarization of the fragments. The electronic wave function of the molecule was used in the adiabatic body frame representation. The rigorous expressions for the fragment state multipoles which have been explicitly derived from the scattering wave function formalism have been used for the case of slow predissociation where a molecule lives in the excited quasibound state much longer than a rotation period. Possible radial nonadiabatic interactions were taken into consideration. The optical excitation of a single rotational branch and the broadband incoherent excitation of all possible rotational branches have been analyzed in detail. The angular momentum polarization of the photofragments has been treated in the high-J limit. The polarization of the photofragment angular momenta predicted by the theory depends on photodissociation mechanism and can in many cases be significant

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)

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

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.

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.

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.

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

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...

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

Predissociation of high-lying Rydberg states of molecular iodine via ion-pair states

Energy Technology Data Exchange (ETDEWEB)

Bogomolov, Alexandr S. [Institute of Chemical Kinetics and Combustion, Institutskaya Str. 3, Novosibirsk 630090 (Russian Federation); Grüner, Barbara; Mudrich, Marcel [Physikalisches Institut, Universität Freiburg, D-79104 Freiburg (Germany); Kochubei, Sergei A. [Institute of Semiconductor Physics, ac. Lavrent' yev ave., 13, Novosibirsk 630090 (Russian Federation); Baklanov, Alexey V. [Institute of Chemical Kinetics and Combustion, Institutskaya Str. 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090 (Russian Federation)

2014-03-28

Velocity map imaging of the photofragments arising from two-photon photoexcitation of molecular iodine in the energy range 73 500–74 500 cm{sup −1} covering the bands of high-lying gerade Rydberg states [{sup 2}Π{sub 1/2}]{sub c}6d;0{sub g}{sup +} and [{sup 2}Π{sub 1/2}]{sub c}6d;2{sub g} has been applied. The ion signal was dominated by the atomic fragment ion I{sup +}. Up to 5 dissociation channels yielding I{sup +} ions with different kinetic energies were observed when the I{sub 2} molecule was excited within discrete peaks of Rydberg states and their satellites in this region. One of these channels gives rise to images of I{sup +} and I{sup −} ions with equal kinetic energy indicating predissociation of I{sub 2} via ion-pair states. The contribution of this channel was up to about 50% of the total I{sup +} signal. The four other channels correspond to predissociation via lower lying Rydberg states giving rise to excited iodine atoms providing I{sup +} ions by subsequent one-photon ionization by the same laser pulse. The ratio of these channels varied from peak to peak in the spectrum but their total ionic signal was always much higher than the signal of (2 + 1) resonance enhanced multi-photon ionization of I{sub 2}, which was previously considered to be the origin of ionic signal in this spectral range. The first-tier E0{sub g}{sup +} and D{sup ′}2{sub g} ion-pair states are concluded to be responsible for predissociation of Rydberg states [{sup 2}Π{sub 1/2}]{sub c}6d;0{sub g}{sup +} and [{sup 2}Π{sub 1/2}]{sub c}6d;2{sub g}, respectively. Further predissociation of these ion-pair states via lower lying Rydberg states gives rise to excited I(5s{sup 2}5p{sup 4}6s{sup 1}) atoms responsible for major part of ion signal. The isotropic angular distribution of the photofragment recoil directions observed for all channels indicates that the studied Rydberg states are long-lived compared with the rotational period of the I{sub 2} molecule.

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.

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

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.

Electronic structure and time-dependent description of rotational predissociation of LiH

DEFF Research Database (Denmark)

Jasik, P.; Sienkiewicz, J. E.; Domsta, J.

2017-01-01

parameters and the experimental ones. The dynamics of the rotational predissociation process of the 11Π state were studied by solving the time-dependent Schrödinger equation. The classical experiment of Velasco [Can. J. Phys., 1957, 35, 1204] on dissociation in the 11Π state is explained for the first time...

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

[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.

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.

Infrared spectroscopy of ionic clusters

International Nuclear Information System (INIS)

Price, J.M.

1990-11-01

This thesis describes new experiments wherein the infrared vibrational predissociation spectra of a number of mass-selected ionic cluster systems have been obtained and analyzed in the 2600 to 4000 cm -1 region. The species studied include: the hydrated hydronium ions, H 3 O + (H 2 O) 3 -10 , ammoniated ammonium ions, NH 4 + (NH 3 ) 1 -10 and cluster ions involving both water and ammonia around an ammonium ion core, (mixed clusters) NH 4 + (NH 3 ) n (H 2 O) m (n+m=4). In each case, the spectra reveal well resolved structures that can be assigned to transitions arising from the vibrational motions of both the ion core of the clusters and the surrounding neutral solvent molecules. 154 refs., 19 figs., 8 tabs

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.

Overtone vibrational spectroscopy in H2-H2O complexes: a combined high level theoretical ab initio, dynamical and experimental study.

Science.gov (United States)

Ziemkiewicz, Michael P; Pluetzer, Christian; Nesbitt, David J; Scribano, Yohann; Faure, Alexandre; van der Avoird, Ad

2012-08-28

First results are reported on overtone (v(OH) = 2 ← 0) spectroscopy of weakly bound H(2)-H(2)O complexes in a slit supersonic jet, based on a novel combination of (i) vibrationally mediated predissociation of H(2)-H(2)O, followed by (ii) UV photodissociation of the resulting H(2)O, and (iii) UV laser induced fluorescence on the nascent OH radical. In addition, intermolecular dynamical calculations are performed in full 5D on the recent ab initio intermolecular potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008)] in order to further elucidate the identity of the infrared transitions detected. Excellent agreement is achieved between experimental and theoretical spectral predictions for the most strongly bound van der Waals complex consisting of ortho (I = 1) H(2) and ortho (I = 1) H(2)O (oH(2)-oH(2)O). Specifically, two distinct bands are seen in the oH(2)-oH(2)O spectrum, corresponding to internal rotor states in the upper vibrational manifold of Σ and Π rotational character. However, none of the three other possible nuclear spin modifications (pH(2)-oH(2)O, pH(2)-pH(2)O, or oH(2)-pH(2)O) are observed above current signal to noise level, which for the pH(2) complexes is argued to arise from displacement by oH(2) in the expansion mixture to preferentially form the more strongly bound species. Direct measurement of oH(2)-oH(2)O vibrational predissociation in the time domain reveals lifetimes of 15(2) ns and <5(2) ns for the Σ and Π states, respectively. Theoretical calculations permit the results to be interpreted in terms of near resonant energy levels and intermolecular alignment of the H(2) and H(2)O wavefunctions, providing insight into predissociation dynamical pathways from these metastable levels.

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.

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

Can Internal Conversion BE Controlled by Mode-Specific Vibrational Excitation in Polyatomic Molecules

Science.gov (United States)

Portnov, Alexander; Epshtein, Michael; Bar, Ilana

2017-06-01

Nonadiabatic processes, dominated by dynamic passage of reactive fluxes through conical intersections (CIs) are considered to be appealing means for manipulating reaction paths. One approach that is considered to be effective in controlling the course of dissociation processes is the selective excitation of vibrational modes containing a considerable component of motion. Here, we have chosen to study the predissociation of the model test molecule, methylamine and its deuterated isotopologues, excited to well-characterized quantum states on the first excited electronic state, S_{1}, by following the N-H(D) bond fission dynamics through sensitive H(D) photofragment probing. The branching ratios between slow and fast H(D) photofragments, the internal energies of their counter radical photofragments and the anisotropy parameters for fast H photofragments, confirm correlated anomalies for predissociation initiated from specific rovibronic states, reflecting the existence of a dynamic resonance in each molecule. This resonance strongly depends on the energy of the initially excited rovibronic states, the evolving vibrational mode on the repulsive S_{1} part during N-H(D) bond elongation, and the manipulated passage through the CI that leads to radicals excited with C-N-H(D) bending and preferential perpendicular bond breaking, relative to the photolyzing laser polarization, in molecules containing the NH_{2} group. The indicated resonance plays an important role in the bifurcation dynamics at the CI and can be foreseen to exist in other photoinitiated processes and to control their outcome.

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.

Improving COIL Efficiency By Iodine Pre-Dissociation Via Corona Discharge In The Transonic Section Of The Secondary Flow

National Research Council Canada - National Science Library

Rosenwaks, Zamik; Barmashenko, Boris

2006-01-01

...: We intend to carry out a comprehensive experimental study of I2 pre-dissociation, based on applying corona discharge in the transonic section of the secondary flow in the COIL supersonic nozzle...

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

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

Science.gov (United States)

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

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

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.

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.

The rotational predissociation of HeH+ energy and lifetime measurements, ch. 3

International Nuclear Information System (INIS)

Locht, R.; Maas, J.G.; Asselt, N.P.F.B. van; Los, J.

1976-01-01

Relative lifetimes and energies above the dissociation limit have been determined for the rotational predissociation of several quasi-bound levels of the X'Σ + state of 4 HeH + . In particular, the lifetimes are very sensitive to the shape of the potential energy curve. These measurements are used to discriminate between two ab initio potential curves which differ by only 0.00004 a.u. (approximately 1 meV). Using the lifetime data, relative population factors were determined for the observed levels

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/

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)

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.

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.

Emission spectra of dimethoxybenzenes by controlled electron impact

International Nuclear Information System (INIS)

Ogawa, Teiichiro; Imasaka, Totaro; Toyoda, Minoru; Tsuji, Masaharu; Ishibashi, Nobuhiko

1975-01-01

The emission spectra of o-, m-, and p-dimethoxybenzenes under controlled electron impact excitation (200 eV) were measured in the 220 - 450 nm region at very low pressures. The photoemissions of the excited parent species and such fragment species as H, CH, CO, and CO + were observed and assigned. The relative intensities of the photoemissions of the parent species were compared with those of the fluorescence spectra (photoexcitation) in an n-hexane solution. The excited parent species, H, and CH were concluded to be produced in one-electron processes; however, the CO + species were assumed to be produced in both one- and two-electron processes, and the relative contributions are evaluated. It was concluded that the rate of the predissociation of o-dimethoxybenzene was faster than those of the other two isomers, and the observed characteristics of o-dimethoxybenzene had something to do with this faster rate. (auth.)

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

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.

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.      

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.)

Infrared spectroscopy of ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Price, J.M. (California Univ., Berkeley, CA (USA). Dept. of Chemistry Lawrence Berkeley Lab., CA (USA))

1990-11-01

This thesis describes new experiments wherein the infrared vibrational predissociation spectra of a number of mass-selected ionic cluster systems have been obtained and analyzed in the 2600 to 4000 cm{sup {minus}1} region. The species studied include: the hydrated hydronium ions, H{sub 3}O{sup +} (H{sub 2}O){sub 3 {minus}10}, ammoniated ammonium ions, NH{sub 4}{sup +}(NH{sub 3}){sub 1 {minus}10} and cluster ions involving both water and ammonia around an ammonium ion core, (mixed clusters) NH{sub 4}{sup +}(NH{sub 3}){sub n}(H{sub 2}O){sub m} (n+m=4). In each case, the spectra reveal well resolved structures that can be assigned to transitions arising from the vibrational motions of both the ion core of the clusters and the surrounding neutral solvent molecules. 154 refs., 19 figs., 8 tabs.

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

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

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

Predissociation of the D 1PIsub(u) state of H2 near threshold

International Nuclear Information System (INIS)

Borondo, F.; Eguiagaray, L.R.; Riera, A.

1982-01-01

A recent calculation of Komarov and Ostrovsky (J. Phys. B.; 12:2485 (1979)) seemed to have settled a controversy regarding the different experimental values of the H(2s)/H(2p) sharing ratio in the predissociation of the D 1 PIsub(u) state of H 2 near threshold. This calculation was based on a correct physical picture of the dissociation process, but the dynamical treatment rests on invalid assumptions. In the present work, a more rigorous quantum mechanical treatment is presented, and a branching ratio of 0.70 is obtained. (author)

Many-body processes in atomic and molecular physics. Progress report, September 1, 1982-August 31, 1983

International Nuclear Information System (INIS)

Chu, S.I.

1983-04-01

Progress is reported in the following areas: (1) development of a powerful semiclassical many-mode Floquet theory for nonperturbative treatment of the multiphoton dynamics of a quantum system interacting with several monochromatic radiation fields, (2) development of analytical quasi-level models for line shape analysis of intense field molecular multiphoton absorption spectra, (3) completion of a high-precision rotatonal predissociation lifetime determination of Ar-H 2 and Ar-HD van der Waals (vdW) molecules, using the complex-coordinate coupled-channel (CCCC) formalisms, and (4) development of the complex quasi-vibrational energy (QVE) and the inhomogeneous differential equation (IDE) approaches for calculating multiphoton dissociation (MPD) rates from highly excited vibrational states of diatomic molecules

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.

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

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.

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.

Excited State Chemistry in the Free Stream of the NASA IHF Arc Jet Facility Observed by Emission Spectroscopy

Science.gov (United States)

Winter, Michael W.; Prabhu, Dinesh K.

2011-01-01

Spectroscopic measurements of non-equilibrium emission were made in the free stream of the 60 megawatts Interaction Heating Facility at NASA Ames Research Center. In the visible near infrared wavelength region, the most prominent emission was from molecular N2, and in the ultra violet region, the spectra were dominated by emission from molecular NO. The only atomic lines observed were those of copper (an erosion product of the electrodes). The bands of the 1st Positive system of N2 (if B is true then A is true) differed significantly from spectra computed spectra assuming only thermal excitation, suggesting overpopulation of the high vibrational states of the B state of N2. Populations of these high vibrational levels (peaking at v (sub upper) equals 13) of the N2 B state were determined by scaling simulated spectra; calculations were performed for each upper vibrational state separately. The experimental-theoretical procedure was repeated for several radial positions away from the nozzle axis to obtain spatial distributions of the upper state populations; rotational symmetry of the flow was assumed in simulations. The overpopulation of the high vibrational levels has been interpreted as the effect of inverse pre-dissociation of neutral atoms in the N2 A state, which populates the N2 B state through a level crossing process at v (sub upper) is greater than 10.

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)

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.

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

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.

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

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.

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)

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.

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

Predissociation of the D /sup 1/PIsub(u) state of H/sub 2/ near threshold

Energy Technology Data Exchange (ETDEWEB)

Borondo, F.; Eguiagaray, L.R.; Riera, A. (Universidad Autonoma de Madrid (Spain). Dept. de Quimica Fisica y Quimica Cuantica)

1982-03-28

A recent calculation of Komarov and Ostrovsky (J. Phys. B.; 12:2485 (1979)) seemed to have settled a controversy regarding the different experimental values of the H(2s)/H(2p) sharing ratio in the predissociation of the D /sup 1/PIsub(u) state of H/sub 2/ near threshold. This calculation was based on a correct physical picture of the dissociation process, but the dynamical treatment rests on invalid assumptions. In the present work, a more rigorous quantum mechanical treatment is presented, and a branching ratio of 0.70 is obtained.

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.

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

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.

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.

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.

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.

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...

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)

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.

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

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)

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

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.

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.

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.

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.

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

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.

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.

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)

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.

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

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.

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

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.

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.

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.

General complex rotated finite-element method for predissociation studies of diatomic molecules: An application on the (1-6)1Σg+ states of H2

International Nuclear Information System (INIS)

Andersson, Stefan; Elander, Nils

2004-01-01

An exterior complex rotated finite element method was applied on the diabatic multichannel Schroedinger equation in order to compute and compare rovibronic energy structures, predissociation widths, and nonradiative lifetimes for levels in the (1-4) (1-5), and (1-6) 1 Σ g + manifolds of H 2 . The rotationless (v,J=0) levels are found to be more or less shifted relative to each other when comparing the results for these three manifolds. The existence of homogeneous spectroscopic perturbations was investigated by studying the rovibronic (v,J=0-10) sequences for energies and level widths. Known experimental and theoretical radiative lifetimes were used to estimate present levels that might be spectroscopically measurable. The computed level widths for the EF, GK, and H electronic levels were generally found to be about two orders of magnitude larger than previously reported [P. Quadrelli, K. Pressler, and L. Woiniewicz, J. Chem. Phys. 93, 4958 (1990)], indicating a somewhat stronger predissociation

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)

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

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

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

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.

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.

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.

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.

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.

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.

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.

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.

Cartesian coupled coherent states simulations: Ne(n)Br2 dissociation as a test case.

Science.gov (United States)

Reed, Stewart K; González-Martínez, Maykel L; Rubayo-Soneira, Jesús; Shalashilin, Dmitrii V

2011-02-07

In this article, we describe coupled coherent states (CCS) simulations of vibrational predissociation of weakly bounded complexes. The CCS method is implemented in the Cartesian frame in a manner that is similar to classical molecular dynamics. The calculated lifetimes of the vibrationally excited Ne-Br(2)(ν) complexes agree with experiment and previous calculations. Although the CCS method is, in principle, a fully quantum approach, in practice it typically becomes a semiclassical technique at long times. This is especially true following dissociation events. Consequently, it is very difficult to converge the quantum calculations of the final Br(2) vibrational distributions after predissociation and of the autocorrelation functions. However, the main advantage of the method is that it can be applied with relative ease to determine the lifetimes of larger complexes and, in order to demonstrate this, preliminary results for tetra- and penta-atomic clusters are reported.

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

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.

Mathematical formulation of temperature fluctuation and control rod vibration in PARR

International Nuclear Information System (INIS)

Ansari, S.A.; Ayazuddin, S.K.

This report describes the mathematical interpretation of experimental neutron noise spectra obtained for PARR core. A one dimensional thermal-hydraulic model of PARR core was developed to calculate the magnitude of neutron noise as a result of fluctuation in the core inlet coolant temperature. The sink structure of the neutron power spectral density as well as the dependence of observed neutron spectra on coolant velocity is also explained by the thermal hydraulic model. An attempt is made to explain the phenomena of control rod vibration by a simple eigen frequency vibration model. The calculated neutron power spectral density due to vibration and temperature noise were added and compared with the experimental power spectra obtained for PARR. (orig./A.B.)

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

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.

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)

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.

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.

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.

Comparative analysis of quasi-linear spectra of organic boron compounds and their heterocyclic and aromatic analogs

International Nuclear Information System (INIS)

Klimova, L.A.; Volkova, V.P.; Kugemova, M.E.; Mikhajlov, B.M.

1976-01-01

Quasiline absorption and luminescence spectra of polycyclic compounds containing boron, nitrogen, or oxygen atoms have been obtained and studied for the first time. Electron-vibrating spectra of these compounds have been compared with the corresponding spectra of nitrogen- and oxygen-containing heterocycles as well as with spectra of their aromatic analog - phenanthrene. Vibrational analysis of the spectra of all the compounds reveals, within the accuracy limit of measurements, the relative closeness of the vibrational frequencies. However, the great difference between the positions of electron transitions points to a change in π-electron structure of the molecules when heteroatoms are introduced. High sensitivity of the frequency of electron transition to structural changes makes it possible to determine the degree of influence of separate heteroatoms

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

Hydrogen bonding in (substituted benzene)·(water)n clusters with n≤4

International Nuclear Information System (INIS)

Barth, H.-D.; Buchhold, K.; Djafari, S.; Reimann, B.; Lommatzsch, U.; Brutschy, B.

1998-01-01

Infrared ion-depletion spectroscopy, a double resonance method combining vibrational predissociation with resonant two-photon ionization (R2PI) spectroscopy, has been applied to study mixed clusters of the type (substituted benzene)·(H 2 O) n with n≤4. The UV chromophores were p-difluorobenzene, fluorobenzene, benzene, toluene, p-xylene and anisole. From the IR depletion spectra in the region of the OH stretching vibrations it could be shown that the water molecules are attached as subclusters to the chromophores. Size and configuration of the subclusters could be deduced from the IR depletion spectra. In the anisole·(H 2 O) 1 a nd 2 complexes the water clusters form an ordinary hydrogen bond to the oxygen atom of the methoxy group. In all other mixed complexes a π-hydrogen bond is formed between one of the free OH groups of a water subcluster and the π-system of the chromophore. According to the strength of this interaction the frequency of the respective absorption band exhibits a characteristic red-shift which could be related to the total atomic charges in the aromatic ring. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

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

Science.gov (United States)

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

2006-04-20

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

Vibrational spectroscopy of shock-compressed fluid N2 and O2

International Nuclear Information System (INIS)

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

1987-01-01

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

Nonadiabatic quantum dynamics and laser control of Br2 in solid argon.

Science.gov (United States)

Accardi, A; Borowski, A; Kühn, O

2009-07-02

A five-dimensional reaction surface-vibronic coupling model is introduced to describe the B- to C-state predissociation dynamics of Br(2) occupying a double substitutional lattice site in a face-centered cubic argon crystal at low temperatures. The quantum dynamics driven by a Franck-Condon vertical excitation is investigated, revealing the role of matrix cage compression for efficient nonadiabatic transitions. Vibrational preexcitation of the Br(2) bond in the electronic ground state can be used to access a different regime of predissociation which does not require substantial matrix compression because the Franck-Condon window shifts into the energetic range of the B-C level crossing. Using optimal control theory, it is shown how vibrational preexcitation can be achieved via a pump-dump-type mechanism involving the repulsive C state.

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.

Wetting effect on optical sum frequency generation (SFG) spectra of D-glucose, D-fructose, and sucrose

Science.gov (United States)

Hieu, Hoang Chi; Li, Hongyan; Miyauchi, Yoshihiro; Mizutani, Goro; Fujita, Naoko; Nakamura, Yasunori

2015-03-01

We report a sum frequency generation (SFG) spectroscopy study of D-glucose, D-fructose and sucrose in the Csbnd H stretching vibration regime. Wetting effect on the SFG spectra was investigated. The SFG spectrum of D-glucose changed from that of α-D-glucose into those of α-D-glucose monohydrate by wetting. The SFG spectra showed evidence of a small change of β-D-fructopyranose into other anomers by wetting. SFG spectra of sucrose did not change by wetting. Assignments of the vibrational peaks in the SFG spectra of the three sugars in the dry and wet states were performed in the Csbnd H stretching vibration region near 3000 cm-1.

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)

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

Molecular Origin of the Vibrational Structure of Ice Ih.

Science.gov (United States)

Moberg, Daniel R; Straight, Shelby C; Knight, Christopher; Paesani, Francesco

2017-06-15

An unambiguous assignment of the vibrational spectra of ice I h remains a matter of debate. This study demonstrates that an accurate representation of many-body interactions between water molecules, combined with an explicit treatment of nuclear quantum effects through many-body molecular dynamics (MB-MD), leads to a unified interpretation of the vibrational spectra of ice I h in terms of the structure and dynamics of the underlying hydrogen-bond network. All features of the infrared and Raman spectra in the OH stretching region can be unambiguously assigned by taking into account both the symmetry and the delocalized nature of the lattice vibrations as well as the local electrostatic environment experienced by each water molecule within the crystal. The high level of agreement with experiment raises prospects for predictive MB-MD simulations that, complementing analogous measurements, will provide molecular-level insights into fundamental processes taking place in bulk ice and on ice surfaces under different thermodynamic conditions.

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

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.

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.

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.

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.

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.

Spectroscopic Observation of Water-Mediated Deformation of the CARBOXYLATE-M2+ (M= Mg, Ca) Contact Ion Pair

Science.gov (United States)

Kelleher, Patrick J.; DePalma, Joseph W.; Johnson, Mark

2016-06-01

The binding of alkaline earth dications to the biologically relevant carboxylate ligand has previously been studied using vibrational sum frequency generation (VSFG) spectroscopy of the air-water interface, infrared multiple photon dissociation (IRMPD) spectroscopy of clusters, and DFT methods. These results suggest the presence of both monodentate and bidentate binding motifs of the M2+ ions to the cayboxyl head groups depending on the extent of solvation. We revisit these systems using vibrational predissociation spectroscopy to measure the gas-phase vibrational spectra of the D2-tagged microhydrated [MgOAc(H2O)n=1-5]+ and [CaOAc(H2O)n=1-6]+ clusters. The spectra show that [MgOAc(H2O)n]+ switches from bidentate to monodentate binding promptly at n = 5, while [CaOAc(H2O)n]+ retains its bidentate attachment such that the sixth water molecule initiates the second solvation shell. The difference in binding behavior between these two divalent metal ions is analyzed in the context of the local acidity of the solvent water molecules and the strength of the metal-carboxylate and metal-water interactions. This cluster study provides insight into the chemical physics underlying the unique and surprising impacts of Mg2+ and Ca2+ on the chemistry mediated by sea spray aerosols. Funding for this work was provided by the NSF's Center for Aerosol Impacts on Climate and the Environment.

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.

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.

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.

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

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.

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.

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.

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.

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...

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.

Using Separable Nonnegative Matrix Factorization Techniques for the Analysis of Time-Resolved Raman Spectra

Science.gov (United States)

Luce, R.; Hildebrandt, P.; Kuhlmann, U.; Liesen, J.

2016-09-01

The key challenge of time-resolved Raman spectroscopy is the identification of the constituent species and the analysis of the kinetics of the underlying reaction network. In this work we present an integral approach that allows for determining both the component spectra and the rate constants simultaneously from a series of vibrational spectra. It is based on an algorithm for non-negative matrix factorization which is applied to the experimental data set following a few pre-processing steps. As a prerequisite for physically unambiguous solutions, each component spectrum must include one vibrational band that does not significantly interfere with vibrational bands of other species. The approach is applied to synthetic "experimental" spectra derived from model systems comprising a set of species with component spectra differing with respect to their degree of spectral interferences and signal-to-noise ratios. In each case, the species involved are connected via monomolecular reaction pathways. The potential and limitations of the approach for recovering the respective rate constants and component spectra are discussed.

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.

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)

Vibrational Mode-Specific Autodetachment and Coupling of CH2CN-

Science.gov (United States)

Lyle, Justin; Mabbs, Richard

2017-06-01

The Cyanomethyl Anion, CH_{2}CN-, and neutral radical have been studied extensively, with several findings of autodetachment about the totally symmetric transition, as well as high resolution experiments revealing symmetrically forbidden and weak vibrational features. We report photoelectron spectra using the Velocity-Mapped Imaging Technique in 1-2 \\wn increments over a range of 13460 to 15384 \\wn that has not been previously examined. These spectra include excitation of the ground state cyanomethyl anion into the direct detachment thresholds of previously reported vibrational modes for the neutral radical. Significant variations from Franck-Condon behavior were observed in the branching ratios for resolved vibrational features for excitation in the vicinity of the thresholds involving the νb{3} and νb{5} modes. These are consistent with autodetachment from rovibrational levels of a dipole bound state acting as a resonance in the detachment continuum. The autodetachment channels involve single changes in vibrational quantum number, consistent with the vibrational propensity rule but in some cases reveal relaxation to a different vibrational mode indicating coupling between the modes and/or a breakdown of the normal mode approximation.

Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

Science.gov (United States)

Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

2014-04-24

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

Vibration monitoring and fault diagnostics of a 45 kW motor

International Nuclear Information System (INIS)

Hafeez, T.; Ahmed, A.; Chohan, G.Y.

2003-01-01

Overheating, high noise and vibrations were observed in a 45 kW induction motor of a chilled water pump in an air conditioning plant. The vibration amplitudes along with phase angles were obtained with the help of a data collector. The vibration spectra obtained was further analyzed to diagnose the problem. The user had reported high vibrations in motor since the day of its installation. The frequency peaks and phase data has revealed the possibility of structural resonance, and misalignment in rotor bearing assembly. The problem of eccentric housing bore on non-drive end NDE that resulted in the misalignment of motor shaft in housing assembly. The spectra and phase data is presented and discussed to diagnose the motor problems. The re-monitoring of motor after rectification of manufacturing fault has confirmed the right diagnoses. (author)

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.

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.

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

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 ...

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

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.

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…

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.

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.

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...

Selective probe of the morphology and local vibrations at carbon nanoasperities

Energy Technology Data Exchange (ETDEWEB)

Fujimori, Toshihiko; Endo, Morinobu; Kaneko, Katsumi [Research Center for Exotic Nanocarbons (JST), Shinshu University, 4-17-1, Wakasato, Nagano-city 380-8553 (Japan); Urita, Koki; Moriguchi, Isamu [Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki-shi, Nagasaki 852-8521 (Japan); Tomanek, David [Physics and Astronomy Department, Michigan State University, East Lansing, Michigan 48824 (United States); Ohba, Tomonori [Department of Chemistry, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522 (Japan)

2012-02-14

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm{sup -1}, which are obscured in regular Raman spectra. Ab initio density functional calculations assign modes in this frequency range to local vibrations at the nanohorn cap resembling the radial breathing mode of fullerenes. Careful interpretation of our SERS spectra indicates presence of caps with 5 or 6 pentagons, which are chemically the most active sites. Changes in the peak intensities and frequencies with time indicate that exposure to laser irradiation may cause structural rearrangements at the cap.

A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

Science.gov (United States)

Ali, Narmeen; Mansha, Asim; Asim, Sadia; Zahoor, Ameer Fawad; Ghafoor, Sidra; Akbar, Muhammad Usman

2018-03-01

This paper deals with combined theoretical and experimental study of geometric, electronic and vibrational properties of 2-chlorothioxanthone (CTX) molecule which is potential photosensitizer. The FT-IR spectrum of CTX in solid phase was recorded in 4000-400 cm-1 region. The UV-Vis. absorption spectrum was also recorded in the laboratory as well as computed at DFT/B3LYP level in five different phases viz. gas, water, DMSO, acetone and ethanol. The quantum mechanics based theoretical IR and Raman spectra were also calculated for the title compound employing HF and DFT functional with 3-21G+, 6-31G+ and 6-311G+, 6-311G++ basis sets, respectively, and assignment of each vibrational frequency has been done on the basis of potential energy distribution (PED). A comparison has been made between theoretical and experimental vibrational spectra as well as for the UV-Vis. absorption spectra. The computed infra red & Raman spectra by DFT compared with experimental spectra along with reliable vibrational assignment based on PED. The calculated electronic properties, results of natural bonding orbital (NBO) analysis, charge distribution, dipole moment and energies have been reported in the paper. Bimolecular quenching of triplet state of CTX in the presence of triethylamine, 2-propanol triethylamine and diazobicyclooctane (DABCO) reflect the interactions between them. The bimolecular quenching rate constant is fastest for interaction of 3CTX in the presence of DABCO reflecting their stronger interactions.

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.

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.

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)

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

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

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 ...

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

[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.

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.

DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

Science.gov (United States)

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

2018-05-01

The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

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.

OD bands in the IR spectra of a deuterated soda-lime-silica glass

Energy Technology Data Exchange (ETDEWEB)

Peuker, C.; Brzezinka, K.W.; Gaber, M.; Kohl, A.; Geissler, H. [Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin (Germany)

2001-07-01

IR spectra of a deuterated glass of the composition (in mol%) 16 Na{sub 2}O . 10 CaO . 74 SiO{sub 2} complete earlier spectroscopic studies on water-poor soda-lime-silica glasses. The approved IR spectroscopic method of the deuterium exchange allows a reliable assignment of the hydroxyl bands also in the case of glasses. By spectra comparison the assignment of the IR bands at 3500 and 2800 cm{sup -1} to hydroxyl groups with different hydrogen bonding is verified. The IR band at about 4500 cm{sup -1} is interpreted as both a combination of the stretching vibrations {nu}O-H and {nu}Si-OH and a combination of the stretching vibration {nu}O-H and the deformation vibration {delta}SiOH. The bands at 1763 and 1602 cm{sup -1} are attributed to combination vibrations of the glass network. (orig.)

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.

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.

Raman Optical Activity and Raman Spectra of Amphetamine Species

DEFF Research Database (Denmark)

Berg, Rolf W.; Shim, Irene; White, Peter Cyril

2012-01-01

Theoretical calculations and preliminary measurements of vibrational Raman optical activity (ROA) spectra of different species of amphetamine (amphetamine and amphetamine-H+) are reported for the first time. The quantum chemical calculations were carried out as hybrid ab initio DFT-molecular orbi......Theoretical calculations and preliminary measurements of vibrational Raman optical activity (ROA) spectra of different species of amphetamine (amphetamine and amphetamine-H+) are reported for the first time. The quantum chemical calculations were carried out as hybrid ab initio DFT...... are employed for identification purposes. The DFT calculations show that the most stable conformations are those allowing for close contact between the aromatic ring and the amine hydrogen atoms. The internal rotational barrier within the same amphetamine enanti- omer has a considerable influence on the Raman...

Conformational and vibrational analysis of 5-hydroxy 2-nitrobenzaldehyde by AB initio hartree-fock, density functional theory calculations

International Nuclear Information System (INIS)

Cinakli, S.; Sert, Y.; Boeyuekata, M.; Ucun, F.

2010-01-01

The vibrational spectra of benzaldehyde and its derivatives have been studied earlier. The substitution of a functional group changes the spectra markedly. Recent spectroscopic studies of the benzaldehyde and their derivatives have been motivated because the vibrational spectra are very useful for understanding of specific biological process and in the analysis of relatively complex systems. The optimized molecular structure, vibrational frequencies and corresponding vibrational assignments, the total energy calculations, relative energies, the mean vibrational deviations of the two planar O-cis and O-trans roomers of 5-Hydroxy 2-nitrobenzaldehydes have been calculated using ab initio Hartree Fock (HF) and Density Functional Theory (B3LYP) with 6-311++G(d,p) basis set. All computations have been performed on personal computer using the Gaussian 03 program package. The calculations were adapted to Cs symmetries of all the molecules. The O-trans rotomers with lower energy of all the molecules have been found as preferential rotomers in the ground state.

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.

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.

Statistical analysis of the variation of floor vibrations in nuclear power plants subject to seismic loads

International Nuclear Information System (INIS)

Jussila, Vilho; Li, Yue; Fülöp, Ludovic

2016-01-01

Highlights: • Floor flexibility plays a non-negligible role in amplifying horizontal vibrations. • COV of in-floor horizontal and vertical acceleration are 0.15–0.25 and 0.25–0.55. • In-floor variation of vibrations is higher in lower floors. • Floor spectra from limited nodes underestimates vibrations by a factor of 1.5–1.75. - Abstract: Floor vibration of a reactor building subjected to seismic loads was investigated, with the aim of quantifying the variability of vibrations on each floor. A detailed 3D building model founded on the bedrock was excited simultaneously in three directions by artificial accelerograms compatible with Finnish ground response spectra. Dynamic simulation for 21 s was carried out using explicit time integration. The extracted results of the simulation were acceleration in several floor locations, transformed to pseudo-acceleration (PSA) spectra in the next stage. At first, the monitored locations on the floors were estimated by engineering judgement in order to arrive at a feasible number of floor nodes for post processing of the data. It became apparent that engineering judgment was insufficient to depict the key locations with high floor vibrations, which resulted in un-conservative vibration estimates. For this reason, a more systematic approach was later considered, in which nodes of the floors were selected with a more refined grid of 2 m. With this method, in addition to the highest PSA peaks in all directions, the full vibration distribution in each floor can be determined. A statistical evaluation of the floor responses was also carried out in order to define floor accelerations and PSAs with high confidence of non-exceedance. The conclusion was that in-floor variability can be as high as 50–60% and models with sufficiently dense node grids should be used in order to achieve a realistic estimate of floor vibration under seismic action. The effects of the shape of the input spectra, damping, and flexibility of the

Statistical analysis of the variation of floor vibrations in nuclear power plants subject to seismic loads

Energy Technology Data Exchange (ETDEWEB)

Jussila, Vilho [VTT Technical Research Centre of Finland Ltd, Kemistintie 3, 02230 Espoo (Finland); Li, Yue [Dept. of Civil Engineering, Case Western Reserve University, Cleveland, OH 44106 (United States); Fülöp, Ludovic, E-mail: ludovic.fulop@vtt.fi [VTT Technical Research Centre of Finland Ltd, Kemistintie 3, 02230 Espoo (Finland)

2016-12-01

Highlights: • Floor flexibility plays a non-negligible role in amplifying horizontal vibrations. • COV of in-floor horizontal and vertical acceleration are 0.15–0.25 and 0.25–0.55. • In-floor variation of vibrations is higher in lower floors. • Floor spectra from limited nodes underestimates vibrations by a factor of 1.5–1.75. - Abstract: Floor vibration of a reactor building subjected to seismic loads was investigated, with the aim of quantifying the variability of vibrations on each floor. A detailed 3D building model founded on the bedrock was excited simultaneously in three directions by artificial accelerograms compatible with Finnish ground response spectra. Dynamic simulation for 21 s was carried out using explicit time integration. The extracted results of the simulation were acceleration in several floor locations, transformed to pseudo-acceleration (PSA) spectra in the next stage. At first, the monitored locations on the floors were estimated by engineering judgement in order to arrive at a feasible number of floor nodes for post processing of the data. It became apparent that engineering judgment was insufficient to depict the key locations with high floor vibrations, which resulted in un-conservative vibration estimates. For this reason, a more systematic approach was later considered, in which nodes of the floors were selected with a more refined grid of 2 m. With this method, in addition to the highest PSA peaks in all directions, the full vibration distribution in each floor can be determined. A statistical evaluation of the floor responses was also carried out in order to define floor accelerations and PSAs with high confidence of non-exceedance. The conclusion was that in-floor variability can be as high as 50–60% and models with sufficiently dense node grids should be used in order to achieve a realistic estimate of floor vibration under seismic action. The effects of the shape of the input spectra, damping, and flexibility of the

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.

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)

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.

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

Infrared photodissociation of van der Waals molecules containing ethylene

International Nuclear Information System (INIS)

Casassa, M.P.; Bomse, D.S.; Janda, K.C.

1981-01-01

Vibrational predissociation line shapes in the n 7 region of the ethylene spectrum are measured for van der Waals molecules of ethylene bound to Ne, Ar, Kr, C 2 H 4 , C 2 F 4 , and larger ethylene clusters. The predissociative rate is very fast for this group of molecules. The vibrationally excited state lifetimes are 0.44, 0.59 and 0.89 x 10 -12 sec for (C 2 H 4 ) 2 , ArxC 2 H 4 , and C 2 H 4 xC 2 F 4 respectively. That the observed line shapes are homogeneous is demonstrated by the fact that a low-power, narrow frequency bandwidth laser can dissociate a large fraction of the initial ensemble of ethylene clusters. The observed transition probability is proportional to the number of ethylene subunits for clusters containing three or fewer ethylene subunits. These observations are interpreted in terms of intramolecular energy flow directly from ethylene n 7 to the weak van der Waals modes of motion

Vibrational multiconfiguration self-consistent field theory: implementation and test calculations.

Science.gov (United States)

Heislbetz, Sandra; Rauhut, Guntram

2010-03-28

A state-specific vibrational multiconfiguration self-consistent field (VMCSCF) approach based on a multimode expansion of the potential energy surface is presented for the accurate calculation of anharmonic vibrational spectra. As a special case of this general approach vibrational complete active space self-consistent field calculations will be discussed. The latter method shows better convergence than the general VMCSCF approach and must be considered the preferred choice within the multiconfigurational framework. Benchmark calculations are provided for a small set of test molecules.

New approach for determination of the influence of long-range order and selected ring oscillations on IR spectra in zeolites

Science.gov (United States)

Mikuła, Andrzej; Król, Magdalena; Mozgawa, Włodzimierz; Koleżyński, Andrzej

2018-04-01

Vibrational spectroscopy can be considered as one of the most important methods used for structural characterization of various porous aluminosilicate materials, including zeolites. On the other hand, vibrational spectra of zeolites are still difficult to interpret, particularly in the pseudolattice region, where bands related to ring oscillations can be observed. Using combination of theoretical and computational approach, a detailed analysis of these regions of spectra is possible; such analysis should be, however, carried out employing models with different level of complexity and simultaneously the same theory level. In this work, an attempt was made to identify ring oscillations in vibrational spectra of selected zeolite structures. A series of ab initio calculations focused on S4R, S6R, and as a novelty, 5-1 isolated clusters, as well as periodic siliceous frameworks built from those building units (ferrierite (FER), mordenite (MOR) and heulandite (HEU) type) have been carried out. Due to the hierarchical structure of zeolite frameworks it can be expected that the total envelope of the zeolite spectra should be with good accuracy a sum of the spectra of structural elements that build each zeolite framework. Based on the results of HF calculations, normal vibrations have been visualized and detailed analysis of pseudolattice range of resulting theoretical spectra have been carried out. Obtained results have been applied for interpretation of experimental spectra of selected zeolites.

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.

On-the-fly ab initio semiclassical dynamics: Emission spectra of oligothiophenes

Science.gov (United States)

Wehrle, Marius; Sulc, Miroslav; Vanicek, Jiri

2014-03-01

We employ the thawed Gaussian approximation (TGA) [E. J. Heller, J. Chem. Phys. 62, 1544 (1975)] within an on-the-fly ab initio (OTF-AI) scheme to calculate the vibrationally resolved emission spectra of oligothiophenes up to five rings. OTF-AI-TGA is efficient enough to treat all vibrational degrees of freedom on an equal footing even in case of 5-oligothiophene (105 vibrational degrees of freedom), thus obviating the need for the crude global harmonic approximation, popular for large system. The experimental emission spectra have been almost perfectly reproduced. In order to provide a deeper insight into the associated physical and chemical processes, we present a systematic approach to assess the importance and to analyze the mutual coupling of individual vibrational degrees of freedom during the dynamics. This allows us to explain the changes in the vibrational line shapes of the oligothiophenes with increasing number of rings. Furthermore, we observe the dynamical interplay between quinoid and aromatic characters of individual rings in the oligothiophene chain during the dynamics and confirm that the quinoid character prevails in the center of the chain. This research was supported by the Swiss NSF Grant No. 200021_124936/1 and NCCR Molecular Ultrafast Science & Technology (MUST), and by the EPFL.

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.

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.

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...

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.

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)

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..

Theoretical Study of Infrared and Raman Spectra of Hydrated Magnesium Sulfate Salts

Science.gov (United States)

Chaban, Galina M.; Huo, Winifred M.; Lee, Timothy J.; Kwak, Dochan (Technical Monitor)

2002-01-01

Harmonic and anharmonic vibrational frequencies, as well as infrared and Raman intensities, are calculated for MgSO4.nH20 (n=1-3). Electronic structure theory at the second order Moller-Plesset perturbation theory (MP2) level with a triple-zeta + polarization (TZP) basis set is used to determine the geometry, properties, and vibrational spectra of pure and hydrated MgSO4 salts. The direct vibrational self-consistent field (VSCF) method and its correlation corrected (CC-VSCF) extension are used to determine anharmonic corrections to vibrational frequencies and intensities for the pure MgSO4 and its complex with one water molecule. Very significant differences are found between vibrational of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies are shifted to the red very significantly (by up to 1500-2000/cm) upon complexation with magnesium sulfate. They should be observed between 1700 and 3000/cm in a region very different from the corresponding O-H stretch frequency region of pure water (3700-3800/cm). In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. They can serve as unique identifiers for the presence of sulfate salts. The predicted infrared and Raman spectra should be of valuable help in the design of future missions and analysis of observed data from the ice surface of Jupiter's moon Europa that possibly contains hydrated MgSO4 salts.

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...

Ab-initio study of structural, vibrational and optical properties of solid oxidizers

Energy Technology Data Exchange (ETDEWEB)

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2016-09-15

We report the structural, elastic and vibrational properties of five ionic-molecular solid oxidizers MNO{sub 3} (M = Li, Na, K) and MClO{sub 3} (M = Na, K). By treating long range electron-correlation effects, dispersion corrected method leads to more accurate predictions of structural properties and phase stability of KNO{sub 3} polymorphs. The obtained elastic moduli show soft nature of these materials and are consistent with Ultrasonic Pulse Echo measurements. We made a complete assignment of vibrational modes which are in good accord with available experimental results. From calculated IR and Raman spectra, it is found that the vibrational frequencies show a red-shift from Li → Na → K (Na → K) and N → Cl for nitrates (chlorates) due to increase in mass of metal and non-metal atoms, respectively. The calculated electronic structure using recently developed Tran-Blaha modified Becke-Johnson potential show that the materials are wide band gap insulators with predominant ionic bonding between M{sup +} (metal) and NO{sub 3}{sup −}/ClO{sub 3}{sup −} ions and covalent bonding (N−O and Cl−O) within nitrate and chlorate anionic group. From the calculated optical spectra, we observe that electric-dipole transitions are due to nitrate/chlorate group below 20 eV and cationic transitions occur above 20 eV. The calculated reflectivity spectra are consistent with the available experimental measurements. - Highlights: • Ground state properties with inclusion of dispersion correction method. • Elastic constants and mechanical properties. • Vibrational spectra and their complete assignment. • Raman and IR spectra. • Electronic structure and optical properties using TB-mBJ potential.

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.

Nonlinear optical and electroabsorption spectra of polydiacetylene crystals and films

Science.gov (United States)

Mukhopadhyay, D.; Soos, Z. G.

1996-01-01

Vibronic structure of nonlinear optical (NLO) coefficients is developed within the Condon approximation, displaced harmonic oscillators, and crude adiabatic states. The displacements of backbone modes of conjugated polymers are taken from vibrational data on the ground and 1B excited state. NLO resonances are modeled by three excitations and transition moments taken from Pariser-Parr-Pople (PPP) theory and optimized to polydiacetylene (PDA) spectra in crystals and films, with blue-shifted 1B exciton. The joint analysis of third-harmonic-generation, two-photon absorption, and nondegenerate four-wave-mixing spectra of PDA crystals and films shows weak two-photon absorption to 2A below 1B, leading to overlapping resonances in the THG spectrum, strong two-photon absorption to an nA state some 35% above 1B, and weak Raman resonances in nondegenerate FWM spectra. The full π-π* spectrum contributes to Stark shifts and field-induced transitions, as shown by PPP results for PDA oligomers. The Stark shift dominates high-resolution electroabsorption (EA) spectra of PDA crystals below 10 K. The close correspondence between EA and the first-derivative I'(ω) of the linear absorption above the 1B exciton in PDA crystals provides an experimental separation of vibrational and electronic contributions that limits any even-parity state in this 0.5 eV interval. An oscillator-strength sum rule is applied to the convergence of PDA oligomers with increasing length, N, and the crystal oscillator strengths are obtained without adjustable parameters. The sum rule for the 1B exciton implies large transition moments to higher-energy Ag states, whose locations in recent models are contrasted to PPP results. Joint analysis of NLO and EA spectra clarifies when a few electronic excitations are sufficient, distinguishes between vibrational and electronic contributions, and supports similar π-electron interactions in conjugated molecules and polymers.

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.

THE HIGH-RESOLUTION EXTREME-ULTRAVIOLET SPECTRUM OF N{sub 2} BY ELECTRON IMPACT

Energy Technology Data Exchange (ETDEWEB)

Heays, A. N. [Leiden Observatory, Leiden University, P.O. Box 9513, 2300 RA Leiden (Netherlands); Ajello, J. M.; Aguilar, A. [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States); Lewis, B. R.; Gibson, S. T., E-mail: heays@strw.leidenuniv.nl [Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200 (Australia)

2014-04-01

We have analyzed high-resolution (FWHM = 0.2 Å) extreme-ultraviolet (EUV, 800-1350 Å) laboratory emission spectra of molecular nitrogen excited by an electron impact at 20 and 100 eV under (mostly) optically thin, single-scattering experimental conditions. A total of 491 emission features were observed from N{sub 2} electronic-vibrational transitions and atomic N I and N II multiplets and their emission cross sections were measured. Molecular emission was observed at vibrationally excited ground-state levels as high as v'' = 17, from the a {sup 1}Π {sub g} , b {sup 1}Π {sub u} , and b'{sup 1}Σ {sub u} {sup +} excited valence states and the Rydberg series c'{sub n} {sub +1} {sup 1}Σ {sub u} {sup +}, c{sub n} {sup 1}Π {sub u} , and o{sub n} {sup 1}Π {sub u} for n between 3 and 9. The frequently blended molecular emission bands were disentangled with the aid of a sophisticated and predictive quantum-mechanical model of excited states that includes the strong coupling between valence and Rydberg electronic states and the effects of predissociation. Improved model parameters describing electronic transition moments were obtained from the experiment and allowed for a reliable prediction of the vibrationally summed electronic emission cross section, including an extrapolation to unobserved emission bands and those that are optically thick in the experimental spectra. Vibrationally dependent electronic excitation functions were inferred from a comparison of emission features following 20 and 100 eV electron-impact collisional excitation. The electron-impact-induced fluorescence measurements are compared with Cassini Ultraviolet Imaging Spectrograph observations of emissions from Titan's upper atmosphere.

Structure, spectra and phase transition in p-nitroanilinium perchlorate crystal

Energy Technology Data Exchange (ETDEWEB)

Marchewka, M.K.; Drozd, M.; Pietraszko, A

2003-07-25

The first X-ray diffraction and vibrational spectroscopic analysis of a novel complex between p-nitroaniline and perchloric acid is reported. The structure was solved in 295 K. Room temperature powder infrared and Raman measurements for the p-nitroanilinium perchlorate (1:1) crystals were carried out. The vibrational spectra in the region of internal vibrations of ions corroborates the X-ray data which show that p-nitroaniline molecule is monoprotonated. DSC measurements on powder sample indicate the phase transition point at about 213 and 208 K for heating and cooling, respectively. No detectable signal was observed during powder test for second harmonic generation.

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.

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

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.

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).

Systematic studies of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher derivative methods: Applications to asymmetric and symmetric top and linear polyatomic molecules

International Nuclear Information System (INIS)

Clabo, D.A. Jr.

1987-04-01

Inclusion of the anharmonicity normal mode vibrations [i.e., the third and fourth (and higher) derivatives of a molecular Born-Oppenheimer potential energy surface] is necessary in order to theoretically reproduce experimental fundamental vibrational frequencies of a molecule. Although ab initio determinations of harmonic vibrational frequencies may give errors of only a few percent by the inclusion of electron correlation within a large basis set for small molecules, in general, molecular fundamental vibrational frequencies are more often available from high resolution vibration-rotation spectra. Recently developed analytic third derivatives methods for self-consistent-field (SCF) wavefunctions have made it possible to examine with previously unavailable accuracy and computational efficiency the anharmonic force fields of small molecules

Systematic studies of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher derivative methods: Applications to asymmetric and symmetric top and linear polyatomic molecules

Energy Technology Data Exchange (ETDEWEB)

Clabo, D.A. Jr.

1987-04-01

Inclusion of the anharmonicity normal mode vibrations (i.e., the third and fourth (and higher) derivatives of a molecular Born-Oppenheimer potential energy surface) is necessary in order to theoretically reproduce experimental fundamental vibrational frequencies of a molecule. Although ab initio determinations of harmonic vibrational frequencies may give errors of only a few percent by the inclusion of electron correlation within a large basis set for small molecules, in general, molecular fundamental vibrational frequencies are more often available from high resolution vibration-rotation spectra. Recently developed analytic third derivatives methods for self-consistent-field (SCF) wavefunctions have made it possible to examine with previously unavailable accuracy and computational efficiency the anharmonic force fields of small molecules.

Raman spectra of Au nanoparticles in polycrystalline LiF film

International Nuclear Information System (INIS)

Kurbatova, N.V.; Galyautdinov, M.F.; Stepanov, A.L.; Ivanov, N.A.; Kolesnikov, S.S.; Papernyj, V.L.

2011-01-01

The modification of the size of gold nanoparticles in LiF matrix during laser annealing was studied fort he first time by Raman spectroscopy. Laser annealing was carried out at the wavelength of the plasmon absorption of gold nanoparticles. The experimental spectra were compared with the calculated modes of in-phase bending vibrations in nanoparticles. The observed effects were discussed from the standpoint of the size quantization of acoustic vibrations in nanostructures. (authors)

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...

Flow induced vibrations of piping system (Vibration sources - Mechanical response of the pipes)

International Nuclear Information System (INIS)

Gibert, R.J.; Axisa, F.; Villard, B.

1978-01-01

In order to design the supports of piping system, an estimation of the vibration induced by the fluid conveyed through the pipes are generally needed. For that purpose it is necessary. To evaluate the power spectra of all the main sources generated by the flow. These sources are located at the singular points of the circuit (enlargements, bends, valves, etc. ...). To calculate the modal parameters of fluid containing pipes. This paper presents: a methodical study of the most current singularities. Inter-correlation spectra of local pressure fluctuation downstream from the singularity and correlation spectra of associated acoustical sources have been measured. A theory of noise generation by unsteady flow in internal acoustics has been developed. All these results are very useful for evaluating the source characteristics in most practical pipes. A comparison between the calculation and the results of an experimental test has shown a good agreement

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.

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.

Raman spectra of thiolated arsenicals with biological importance.

Science.gov (United States)

Yang, Mingwei; Sun, Yuzhen; Zhang, Xiaobin; McCord, Bruce; McGoron, Anthony J; Mebel, Alexander; Cai, Yong

2018-03-01

Surface enhanced Raman scattering (SERS) has great potential as an alternative tool for arsenic speciation in biological matrices. SERS measurements have advantages over other techniques due to its ability to maintain the integrity of arsenic species and its minimal requirements for sample preparation. Up to now, very few Raman spectra of arsenic compounds have been reported. This is particularly true for thiolated arsenicals, which have recently been found to be widely present in humans. The lack of data for Raman spectra in arsenic speciation hampers the development of new tools using SERS. Herein, we report the results of a study combining the analysis of experimental Raman spectra with that obtained from density functional calculations for some important arsenic metabolites. The results were obtained with a hybrid functional B3LYP approach using different basis sets to calculate Raman spectra of the selected arsenicals. By comparing experimental and calculated spectra of dimethylarsinic acid (DMA V ), the basis set 6-311++G** was found to provide computational efficiency and precision in vibrational frequency prediction. The Raman frequencies for the rest of organoarsenicals were studied using this basis set, including monomethylarsonous acid (MMA III ), dimethylarsinous acid (DMA III ), dimethylmonothioarinic acid (DMMTA V ), dimethyldithioarsinic acid (DMDTA V ), S-(Dimethylarsenic) cysteine (DMA III (Cys)) and dimethylarsinous glutathione (DMA III GS). The results were compared with fingerprint Raman frequencies from As─O, As─C, and As─S obtained under different chemical environments. These fingerprint vibrational frequencies should prove useful in future measurements of different species of arsenic using SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

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.

Infrared and Raman Spectra of and Isotopomers: A DFT-PT2 Anharmonic Study

Directory of Open Access Journals (Sweden)

Andrea Alparone

2013-01-01

Full Text Available IR and Raman spectra of selenophene and of its perdeuterated isotopomer have been obtained in gas phase through density-functional theory (DFT computations. Vibrational wavenumbers have been calculated using harmonic and anharmonic second-order perturbation theory (PT2 procedures with the B3LYP method and the 6-311 basis set. Anharmonic overtones have been determined by means of the PT2 method. The introduction of anharmonic terms decreases the harmonic wavenumbers, giving a significantly better agreement with the experimental data. The most significant anharmonic effects occur for the C–H and C–D stretching modes, the observed H/D isotopic wavenumber redshifts being satisfactorily reproduced by the PT2 computations within 6–20 cm−1 (1–3%. In the spectral region between 500 cm−1 and 1500 cm−1, the IR spectra are dominated by the out-of-plane C–H (C–D bending transition, whereas the Raman spectra are mainly characterized by a strong peak mainly attributed to the C=C + C–C bonds stretching vibration with the contribution of the in-plane C–H (C–D bending deformation. The current results confirm that the PT2 approach combined with the B3LYP/6-311 level of calculation is a satisfactory choice for predicting vibrational spectra of cyclic molecules.

Mössbauer forward scattering spectra of ferromagnets in radio-frequency magnetic field

Directory of Open Access Journals (Sweden)

A. Ya. Dzyublik

2012-03-01

Full Text Available The transmission of Mössbauer radiation through a thick ferromagnetic crystal, subjected to the radio-frequency (rf magnetic field, is studied. A quantum-mechanical dynamical scattering theory is developed, taking into account both the periodical reversals of the magnetic field at the nuclei and their coherent vibrations. The Mössbauer forward scattering (FS spectra of the weak ferromagnet FeBO3 exposed to the rf field are measured. It is discovered that the coherent gamma wave in the crystal, interacting with Mössbauer nuclei, absorbs or emits only couples of the rf photons. As a result, the FS spectra consist of equidistant lines spaced by twice the frequency of the rf field in contrast to the absorption spectra. Our experimental data and calculations well agree if we assume that the hyperfine field at the nuclei in FeBO3 periodically reverses and there are no coherent vibrations.

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...

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...

Energy spectra of vibron and cluster models in molecular and nuclear systems

Science.gov (United States)

Jalili Majarshin, A.; Sabri, H.; Jafarizadeh, M. A.

2018-03-01

The relation of the algebraic cluster model, i.e., of the vibron model and its extension, to the collective structure, is discussed. In the first section of the paper, we study the energy spectra of vibron model, for diatomic molecule then we derive the rotation-vibration spectrum of 2α, 3α and 4α configuration in the low-lying spectrum of 8Be, 12C and 16O nuclei. All vibrational and rotational states with ground and excited A, E and F states appear to have been observed, moreover the transitional descriptions of the vibron model and α-cluster model were considered by using an infinite-dimensional algebraic method based on the affine \\widehat{SU(1,1)} Lie algebra. The calculated energy spectra are compared with experimental data. Applications to the rotation-vibration spectrum for the diatomic molecule and many-body nuclear clusters indicate that there are solvable models and they can be approximated very well using the transitional theory.

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)

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

Vibrational Energy Distribution Analysis (VEDA): Scopes and limitations

Science.gov (United States)

Jamróz, Michał H.

2013-10-01

The principle of operations of the VEDA program written by the author for Potential Energy Distribution (PED) analysis of theoretical vibrational spectra is described. Nowadays, the PED analysis is indispensible tool in serious analysis of the vibrational spectra. To perform the PED analysis it is necessary to define 3N-6 linearly independent local mode coordinates. Already for 20-atomic molecules it is a difficult task. The VEDA program reads the input data automatically from the Gaussian program output files. Then, VEDA automatically proposes an introductory set of local mode coordinates. Next, the more adequate coordinates are proposed by the program and optimized to obtain maximal elements of each column (internal coordinate) of the PED matrix (the EPM parameter). The possibility for an automatic optimization of PED contributions is a unique feature of the VEDA program absent in any other programs performing PED analysis.

Vibrational spectroscopic study of cationic phosphorus dendrimers with aminoethylpiperidine terminal groups

Science.gov (United States)

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

2018-04-01

Two generations of phosphoric dendrimers with piperidine functional groups were synthesized for use in biology and medicine. Neutral samples are soluble in organic solvents but after protonation these dendrimers become water soluble and can be used for biological experiments. The FTIR and FT Raman spectra of two generations of dendrimers Gi constructed from the cyclotriphosphazene core, repeating units sbnd Osbnd C6H4sbnd CHdbnd Nsbnd N(CH3)sbnd P(S)molecular structure and vibrational spectra of the first generation dendrimer was performed by the method of DFT. This molecule has flat, repeating units and a plane of symmetry passing through the core. The calculation of the distribution of potential energy made it possible to classify the bands in the experimental spectra of dendrimers. Amine groups are manifested in the form of a band of NH stretching vibrations at 3389 cm-1 in the IR spectrum of G1. NH+ stretching bands located at 2646 and 2540 cm-1 in the IR spectrum of G2. The stretching vibrations of NH+ groups are noticeably shifted to low frequencies due to the formation of a hydrogen bond with the chlorine atom. The line at 1575 cm-1 in the Raman spectrum of G1 is characteristic for repeating units.

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.

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

International Nuclear Information System (INIS)

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

1987-01-01

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

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.

Spectroscopic and vibrational analysis of the methoxypsoralen system: A comparative experimental and theoretical study

Science.gov (United States)

Liu, Y.; Yuan, H.; Vo-Dinh, T.

2013-03-01

Raman spectra measurements and density functional theory (DFT) calculations were performed to investigate three psoralens: 5-amino-8-methoxypsoralen (5-A-8-MOP), 5-methoxypsoralen (5-MOP) and 8-methoxypsoralen (8-MOP) with the aim of differentiating these similar bioactive molecules. The Raman spectra were recorded in the region 300-3500 cm-1. All three psoralens were found to have similar Raman spectrum in the region 1500-1650 cm-1. 5-A-8-MOP can be easily differentiated from 5-MOP or 8-MOP based on the Raman spectrum. The Raman spectrum differences at 651 and 795 cm-1 can be used to identify 5-MOP from 8-MOP. The theoretically computed vibrational frequencies and relative peak intensities were compared with experimental data. DFT calculations using the B3LYP method and 6-311++G(d,p) basis set were found to yield results that are very comparable to experimental 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.

The millimeter-wave spectrum of highly vibrationally excited SiO

International Nuclear Information System (INIS)

Mollaaghababa, R.; Gottlieb, C.A.; Vrtilek, J.M.; Thaddeus, P.

1991-01-01

The millimeter-wave rotational spectra of SiO in high vibrational states (v = 0-40) in its electronic ground state were measured between 228 and 347 GHz in a laboratory discharge through SiH4 and CO. On ascending the vibrational ladder, populations decline precipitously for the first few levels, with a vibrational temperature of about 1000 K; at v of roughly 3, however, they markedly flatten out, and from there to v of roughly 40 the temperature is of the order of 10,000 K. With the Dunham coefficients determined here, the rotational spectrum of highly vibrationally excited SiO can now be calculated into the far-infrared to accuracies required for radioastronomy. Possible astronomical sources of highly vibrationally excited SiO are certain stellar atmospheres, ultracompact H II regions, very young supernova ejecta, and dense interstellar shocks. 16 refs

Synthesis and vibrational spectrum of antimony phosphate, SbPO4.

Science.gov (United States)

Brockner, Wolfgang; Hoyer, Lars P

2002-07-01

SbPO4 was synthesized via a new route by reacting antimony metal with meta-phosphoric acid, (HPO3)n at high temperatures. The Raman and IR spectra of the title compound were recorded and the vibrational modes assigned on the basis of a factor group analysis. The internal vibrations are derived from tetrahedral PO4 units (approaching Sb[PO4]) by the correlation method, although the structure is polymeric and not ionic.

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.

Tensor-decomposed vibrational coupled-cluster theory: Enabling large-scale, highly accurate vibrational-structure calculations

Science.gov (United States)

Madsen, Niels Kristian; Godtliebsen, Ian H.; Losilla, Sergio A.; Christiansen, Ove

2018-01-01

A new implementation of vibrational coupled-cluster (VCC) theory is presented, where all amplitude tensors are represented in the canonical polyadic (CP) format. The CP-VCC algorithm solves the non-linear VCC equations without ever constructing the amplitudes or error vectors in full dimension but still formally includes the full parameter space of the VCC[n] model in question resulting in the same vibrational energies as the conventional method. In a previous publication, we have described the non-linear-equation solver for CP-VCC calculations. In this work, we discuss the general algorithm for evaluating VCC error vectors in CP format including the rank-reduction methods used during the summation of the many terms in the VCC amplitude equations. Benchmark calculations for studying the computational scaling and memory usage of the CP-VCC algorithm are performed on a set of molecules including thiadiazole and an array of polycyclic aromatic hydrocarbons. The results show that the reduced scaling and memory requirements of the CP-VCC algorithm allows for performing high-order VCC calculations on systems with up to 66 vibrational modes (anthracene), which indeed are not possible using the conventional VCC method. This paves the way for obtaining highly accurate vibrational spectra and properties of larger molecules.

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.

Raman study of vibrational dynamics of aminopropylsilanetriol in gas phase

Science.gov (United States)

Volovšek, V.; Dananić, V.; Bistričić, L.; Movre Šapić, I.; Furić, K.

2014-01-01

Raman spectrum of aminopropylsilanetriol (APST) in gas phase has been recorded at room temperature in macro chamber utilizing two-mirror technique over the sample tube. Unlike predominantly trans molecular conformation in condensed phase, the spectra of vapor show that the molecules are solely in gauche conformation with intramolecular hydrogen bond N⋯Hsbnd O which reduces the molecular energy in respect to trans conformation by 0.152 eV. The assignment of the molecular spectra based on the DFT calculation is presented. The strong vibrational bands at 354 cm-1, 588 cm-1 and 3022 cm-1 are proposed for verifying the existence of the ring like, hydrogen bonded structure. Special attention was devoted to the high frequency region, where hydrogen bond vibrations are coupled to stretchings of amino and silanol groups.

Use of Directional Spectra for Detection of Engine Cylinder Power Fault

Directory of Open Access Journals (Sweden)

Chong-Won Lee

1997-01-01

Full Text Available A diagnostic method, which uses the two-sided directional power spectra of complex-valued engine vibration signals, is presented and tested with four-cylinder compression and spark ignition engines for the diagnosis of cylinder power faults. As spectral estimators, the maximum likelihood and FFT methods are compared, and the multi-layer neural network is employed for pattern recognition. Experimental results show that the success rate for identifying the misfired cylinder is much higher with the use of two-sided directional power spectra than conventional one-sided power spectra.

Temperature Dependence of Polarized Low Wavenumber Raman Spectra of Aminopropylsilanetriol Polymer

International Nuclear Information System (INIS)

V, Volovsek; L, Bistrcic; K, Furic; V, Daanic; I, Movre Sapic

2006-01-01

Low wavenumber polarized Raman spectra of aminopropylsilanetriol (APST) polymer deposited on PVC substrate were measured in the temperature range from 300 K to 78 K. In the low wavenumber Raman spectra of these samples a very strong Bose band was observed. The best results in modeling the low wavenumber Raman spectra were achieved with the exponential correlation function of disorder G dis (ν) = exp(-r/R c )using three contributions: transversal and longitudinal acoustic phonons and molecular vibration. Results suggest medium range ordered ladder structure, stacked in layers with different orientations of ladders

Transformation of potential energy surfaces for estimating isotopic shifts in anharmonic vibrational frequency calculations

Energy Technology Data Exchange (ETDEWEB)

Meier, Patrick; Oschetzki, Dominik; Rauhut, Guntram, E-mail: rauhut@theochem.uni-stuttgart.de [Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); Berger, Robert [Clemens-Schöpf Institut für Organische Chemie and Biochemie, Technische Universität Darmstadt, Petersenstrasse 22, 64287 Darmstadt (Germany)

2014-05-14

A transformation of potential energy surfaces (PES) being represented by multi-mode expansions is introduced, which allows for the calculation of anharmonic vibrational spectra of any isotopologue from a single PES. This simplifies the analysis of infrared spectra due to significant CPU-time savings. An investigation of remaining deviations due to truncations and the so-called multi-level approximation is provided. The importance of vibrational-rotational couplings for small molecules is discussed in detail. In addition, an analysis is proposed, which provides information about the quality of the transformation prior to its execution. Benchmark calculations are provided for a set of small molecules.

The spectra of conical bubble sonoluminescence in 1,2-propanediol and glycol

International Nuclear Information System (INIS)

He Shoujie; Jing Ha; Li Xuechen; Li Qing; Dong Lifang; Wang, Long

2007-01-01

A conical bubble straight tube apparatus was set up to study sonoluminescence. The spectra of conical bubble sonoluminescence for 1,2-propanediol and glycol were detected. The results show that the luminescence is intense, and the spectra consist of a broad background on which five clear sequences of Swan bands and three sequences of the B 2 Σ + → X 2 Σ + transition of CN are superimposed. A band assigned to the A 2 Δ → X 2 Π transition of CH was also measured and the vibrational and rotational structures of Swan bands could be resolved. The origin of the C* 2 and C 2 H* is discussed. Finally, the achieved molecular vibrational temperature is estimated to be about 5400 ± 350 K

Molecular ion photofragment spectroscopy

International Nuclear Information System (INIS)

Bustamente, S.W.

1983-11-01

A new molecular ion photofragment spectrometer is described which features a supersonic molecular beam ion source and a radio frequency octapole ion trap interaction region. This unique combination allows several techniques to be applied to the problem of detecting a photon absorption event of a molecular ion. In particular, it may be possible to obtain low resolution survey spectra of exotic molecular ions by using a direct vibrational predissociation process, or by using other more indirect detection methods. The use of the spectrometer is demonstrated by measuring the lifetime of the O 2 + ( 4 π/sub u/) metastable state which is found to consist of two main components: the 4 π/sub 5/2/ and 4 π/sub -1/2/ spin components having a long lifetime (approx. 129 ms) and the 4 π/sub 3/2/ and 4 π/sub 1/2/ spin components having a short lifetime (approx. 6 ms)

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

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.

Analysis of aggregate optical spectra using moments. Application to the purple membrane of halobacterium halobium

International Nuclear Information System (INIS)

Hemenger, R.P.

1978-01-01

The problem of extracting structural information from the optical spectra of aggregates of molecules interacting through their electronic transitions is studied. One serious difficulty common to all approaches to this problem is that of properly taking into account the effects of molecular vibrations. A series of exact relations derived previously which are correct with regard to molecular vibrations provide a number of independent, explicit connections between aggregate geometrical parameters and moments of experimental spectra. It is shown that, by applying these moment relations to the optical absorption and circular dichroism spectra of simple aggregates, a complete set of equations can be found, i.e., enough equations can be found to solve for all of the geometrical parameters which enter into the expressions for absorption and circular dichroism spectra. This procedure is applied in some detail to the purple membrane of Halobacterium halobium. The results are completely consistent with what is known about its structure

Photoionization of Ar2 at high resolution

International Nuclear Information System (INIS)

Dehmer, P.M.

1982-01-01

The relative photoionization cross section of Ar 2 was determined at a resolution of 0.07 A in the wavelength region from 800 to 850 A using a new photoionization mass spectrometer that combines a high intensity helium continuum lamp with a free supersonic molecular beam source. In the region studied, the photoionization cross section is dominated by autoionization of molecular Rydberg states, and the structure is diffuse owing to the combined effects of autoionization and predissociation. The molecular photoionization spectrum is extremely complex and shows little resemblence either to the corresponding atomic spectrum (indicating that the spectrum of the dimer is not simply a perturbed atomic spectrum) or to the molecular absorption spectrum at longer wavelengths. The regular vibrational progressions seen at longer wavelengths are absent above the first ionization potential. Detailed spectroscopic analysis is possible for only a small fraction of the observed features; however, vibrational intervals of 50--100 cm -1 suggest that some of the Rydberg states have B 2 Pi/sub 3/2g/ ionic cores. A comparison of the absorption and photoionization spectra shows that, at wavelengths shorter than approx.835 A, many of the excited states decay via mechanisms other than autoionization

FT-IR, FT-Raman spectra and DFT calculations of melaminium perchlorate monohydrate

Science.gov (United States)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

2013-08-01

Melaminium perchlorate monohydrate (MPM), an organic material has been synthesized by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MPM crystal belongs to triclinic system with space group P-1. FTIR and FT Raman spectra are recorded at room temperature. Functional group assignment has been made for the melaminium cations and perchlorate anions. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory (DFT) calculations using Firefly (PC GAMESS) version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with experimental values. The assignment of the bands has been made on the basis of the calculated PED. The Mulliken charges, HOMO-LUMO orbital energies are analyzed directly from Firefly program log files and graphically illustrated. HOMO-LUMO energy gap and other related molecular properties are also calculated. The theoretically constructed FT-IR and FT-Raman spectra of MPM coincide with the experimental one. The chemical structure of the compound has been established by 1H and 13C NMR spectra. No detectable signal was observed during powder test for second harmonic generation.

Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

KAUST Repository

Fonari, A.; Corbin, N. S.; Vermeulen, D.; Goetz, K. P.; Jurchescu, O. D.; McNeil, L. E.; Bredas, Jean-Luc; Coropceanu, V.

2015-01-01

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoreticalRaman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

KAUST Repository

Fonari, A.

2015-12-10

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoreticalRaman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

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.

Infrared and Raman Spectra of Magnesium Ammonium Phosphate Hexahydrate (Struvite) and its Isomorphous Analogues. VIII. Spectra of Protiated and Partially Deuterated Magnesium Rubidium Phosphate Hexahydrate and Magnesium Thallium Phosphate Hexahydrate.

Science.gov (United States)

Soptrajanov, Bojan; Cahil, Adnan; Najdoski, Metodija; Koleva, Violeta; Stefov, Viktor

2011-09-01

The infrared and Raman spectra of magnesium rubidium phosphate hexahydrate MgRbPO4 • 6H2O and magnesium thallium phosphate hexahydrate, MgTlPO4 • 6H2O were recorded at room temperature (RT) and the boiling temperature of liquid nitrogen (LNT). To facilitate their analysis, also recorded were the spectra of partially deuterated analogues with varying content of deuterium. The effects of deuteration and those of lowering the temperature were the basis of the conclusions drawn regarding the origin of the observed bands which were assigned to vibrations which are predominantly localized in the water molecules (four crystallographically different types of such molecules exist in the structures) and those with PO43- character. It was concluded that in some cases coupling of phosphate and water vibrations is likely to take place. The appearance of the infrared spectra in the O-H stretching regions of the infrared spectra is explained as being the result of an extensive overlap of bands due to components of the fundamental stretching modes of the H2O units with a possible participation of bands due to second-order transitions. A broad band reminiscent of the B band of the well-known ABC trio characteristic of spectra of substances containing strong hydrogen bonds in their structure was found around 2400 cm-1 in the infrared spectra of the two studied compounds.

Effect of intermolecular hydrogen bonding, vibrational analysis and molecular structure of 4-chlorobenzothioamide

Science.gov (United States)

Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

2013-09-01

In the present work, the experimental and theoretical vibrational spectra of 4-chlorobenzothioamide were investigated. The FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of 4-chlorobenzothioamide in the solid phase were recorded. The geometric parameters (bond lengths and bond angles), vibrational frequencies, Infrared and Raman intensities of the title molecule in the ground state were calculated using ab initio Hartree-Fock and density functional theory (B3LYP) methods with the 6-311++G(d,p) basis set for the first time. The optimized geometric parameters and the theoretical vibrational frequencies were found to be in good agreement with the corresponding experimental data and with the results found in the literature. The vibrational frequencies were assigned based on the potential energy distribution using the VEDA 4 program. The dimeric form of 4-chlorobenzothioamide was also simulated to evaluate the effect of intermolecular hydrogen bonding on the vibrational frequencies. It was observed that the Nsbnd H stretching modes shifted to lower frequencies, while the in-plane and out-of-plane bending modes shifted to higher frequencies due to the intermolecular Nsbnd H⋯S hydrogen bond. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies and diagrams were presented.

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 C_2v 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 C_s and C₂ symmetry, and for para-xylene these conformers have C_2v or C_2h 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 C_s conformer for meta-xylene and the C_2v 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.

Stochastic aspects of two-dimensional vibration diagnostics

International Nuclear Information System (INIS)

Pazsit, I.; Antonopoulos-Domis, M.; Gloeckler, O.

1985-01-01

The aim of this paper is to investigate the stochastic features of two-dimensional lateral damped oscillations of PWR core internals, that are induced by random force components. It is also investigated how these vibrating components, or the forces giving rise to the vibrations could be diagnosed through the analysis of displacement or neutron noise signals. The approach pursued here is to select a realisation of the random force components, then the equations of the motion are integrated and the time history of displacement components is obtained. From here various statistical descriptors of the motion, such as trajectory pattern, spectra and PDF functions, etc. can be calculated. It was investigated how these statistical descriptors depend on the characteristics of the driving force for both stationary and non-stationary cases. A conclusion of possible diagnostical relevance is that, under certain circumstances, the PDF functions could be an indicator of whether a particular peak in the corresponding power spectra belongs to a resonance in system transfer or rather a resonance in the external driving force. (author)

Stochastic aspects of two-dimensional vibration diagnostics

International Nuclear Information System (INIS)

Pazsit, I.; Antonopoulos-Domis, M.; Glockler, O.

1984-01-01

The aim of this paper is to investigate the stochastic features of two-dimensional lateral damped oscillations of PWR core internals that are induced by random force components. It is also investigated how these vibrating components, or the forces giving rise to the vibrations, could be diagnosed through the analysis of displacement or neutron noise signals. The approach pursued here is to select a realisation of the random force components, then the equations of the motion are integrated and the time history of displacement components is obtained. From here various statistical descriptors of the motion, such as trajectory pattern, spectra and PDF functions etc., can be calculated. It was investigated how these statistical descriptors depend on the characteristics of the driving force for both stationary and non-stationary cases. A conclusion of possible diagnostical relevance is that, under certain circumstances, the PDF functions could be an indicator of whether a particular peak in the corresponding power spectra belongs to a resonance in system transfer or rather a resonance in the external driving force

Stochastic aspects of two-dimensional vibration diagnostics

International Nuclear Information System (INIS)

Pazsit, I.; Gloeckler, O.

1984-01-01

The aim of this paper is to investigate the stochastic features of two-dimensional lateral damped oscillations of PWR core internals that are induced by random force components. It is also investigated how these vibrating components, or the forces giving rise to the vibrations, could be diagnosed through the analysis of displacement or neutron noise signals. The approach pursued here is to select a realisation of the random force components, then the equations of the motion ar integrated and the time history of displacement components is obtained. From here various statistical descriptors of the motion, such as trajectory pattern, spectra and PDF functions etc., can be calculated. It was investigated how these statistical descriptors depend on the characteristics of the driving force for both stationary and non-stationary cases. A conclusion of possible diagnostical relevance is that, under certain circumstances, the PDF functions could be an indicator of whether a particular peak in the corresponding power spectra belongs to a resonance in system transfer or rather a resonance in the external driving force. (author)

Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Atsushi; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture 2500 Hassaka, Hikone, Shiga, 522-8533 (Japan)

2016-02-01

Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

Path integral Liouville dynamics: Applications to infrared spectra of OH, water, ammonia, and methane

International Nuclear Information System (INIS)

Liu, Jian; Zhang, Zhijun

2016-01-01

Path integral Liouville dynamics (PILD) is applied to vibrational dynamics of several simple but representative realistic molecular systems (OH, water, ammonia, and methane). The dipole-derivative autocorrelation function is employed to obtain the infrared spectrum as a function of temperature and isotopic substitution. Comparison to the exact vibrational frequency shows that PILD produces a reasonably accurate peak position with a relatively small full width at half maximum. PILD offers a potentially useful trajectory-based quantum dynamics approach to compute vibrational spectra of molecular systems

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.

Photodissociation of HCN and HNC isomers in the 7-10 eV energy range

Energy Technology Data Exchange (ETDEWEB)

Chenel, Aurelie; Roncero, Octavio, E-mail: octavio.roncero@csic.es [Instituto de Física Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, 28006 Madrid (Spain); Aguado, Alfredo [Departamento de Química Física Aplicada (UAM), Unidad Asociada a IFF-CSIC, Facultad de Ciencias Módulo 14, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Agúndez, Marcelino; Cernicharo, José [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, 28049 Cantoblanco (Spain)

2016-04-14

The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereafter electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation.

Temperature dependence of low-frequency polarized Raman scattering spectra in TlInS{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Paucar, Raul; Wakita, Kazuki [Electronics and Computer Engineering, Chiba Institute of Technology, Chiba (Japan); Shim, YongGu; Mimura, Kojiro [Graduate School of Engineering, Osaka Prefecture University, Osaka (Japan); Alekperov, Oktay; Mamedov, Nazim [Institute of Physics, Azerbaijan National Academy of Sciences, Baku (Azerbaijan)

2017-06-15

In this work, we examined phase transitions in the layered ternary thallium chalcogenide TlInS{sub 2} by studying the temperature dependence of polarized Raman spectra with the aid of the Raman confocal microscope system. The Raman spectra were measured over the temperature range of 77-320 K (which includes the range of successive phase transitions) in the low-frequency region of 35-180 cm{sup -1}. The optical phonons that showed strong temperature dependence were identified as interlayer vibrations related to phase transitions, while the phonons that showed weak temperature dependence were identified as intralayer vibrations. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

DEFF Research Database (Denmark)

Schrøder, Sidsel Dahl

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

Preparation and infrared spectra of differently deuterated tetramethyl-derivatives of the IV. main group

International Nuclear Information System (INIS)

Biedermann, S.

1972-01-01

19 different deuterated tetramethyl derivates of the type (CH 3 )sub(4-n)M(CH 3 )sub(n) of C, Si, Ge, Sn and Pb were prepared. Gas cuvettes with polyethylene, NaCl and KBr windows were used to absorb the infra-red spectra, the IR equipment Beckman IR 11 and IR 12 were used. The infra-red spectra of the above mentioned compounds were indicated from 33 to 4,000 cm -1 , the ground, upper and combination vibrations assigned, the PR separations of the partly well resolved rotation-vibration outlines determined and were compared with the calculated PR separations. The revision of the correlations performed by Graham for γsub(s)CH 3 and γsub(as)CH 3 in the race of vibration F 2 with Sn(CH 3 ) 4 and Pb(CH 3 ) 4 and the proposed one with C(CH 3 ) 4 , Si(CH 3 ) 4 and Ge(CH 3 ) 4 could be disproved by the new experimental results. (FW) [de

Vibrational Spectroscopic Studies of Tenofovir Using Density Functional Theory Method

Directory of Open Access Journals (Sweden)

G. R. Ramkumaar

2013-01-01

Full Text Available A systematic vibrational spectroscopic assignment and analysis of tenofovir has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis was aided by electronic structure calculations—hybrid density functional methods (B3LYP/6-311++G(d,p, B3LYP/6-31G(d,p, and B3PW91/6-31G(d,p. Molecular equilibrium geometries, electronic energies, IR intensities, and harmonic vibrational frequencies have been computed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties such as HOMO and LUMO energies and were determined by time-dependent DFT (TD-DFT method. The geometrical, thermodynamical parameters, and absorption wavelengths were compared with the experimental data. The B3LYP/6-311++G(d,p-, B3LYP/6-31G(d,p-, and B3PW91/6-31G(d,p-based NMR calculation procedure was also done. It was used to assign the 13C and 1H NMR chemical shift of tenofovir.

The Shock and Vibration Bulletin. Part 2. Measurement Techniques and Data Analysis, Dynamic Measurements, Vibration and Acoustics

Science.gov (United States)

1980-09-01

Smallwood and D. L. Gregory, Sandia Laboratories, Albuquerque, NM A NEW METHOD OF IMPROVING SPECTRA SHAPING IN REVERBERANT CHAMBERS...DAMPING M. M. Wallace and C. W. Bert, The University of Oklahoma, Norman , OK CONTRIBUTIONS TO THE DYNAMIC ANALYSIS OF MAGLEV VEHICLES ON ELEVATED GUIDEWAYS...RANDOM VIBRATION EXTRENAL CONTROL STRATEGY D. 0. Smallwood D. L. Gregory Sandia Laboratories Albuquerque, NM This paper discusses the theoretical basis for

Nonplanar tertiary amides in rigid chiral tricyclic dilactams. Peptide group distortions and vibrational optical activity.

Science.gov (United States)

Pazderková, Markéta; Profant, Václav; Hodačová, Jana; Sebestík, Jaroslav; Pazderka, Tomáš; Novotná, Pavlína; Urbanová, Marie; Safařík, Martin; Buděšínský, Miloš; Tichý, Miloš; Bednárová, Lucie; Baumruk, Vladimír; Maloň, Petr

2013-08-22

We investigate amide nonplanarity in vibrational optical activity (VOA) spectra of tricyclic spirodilactams 5,8-diazatricyclo[6,3,0,0(1,5)]undecan-4,9-dione (I) and its 6,6',7,7'-tetradeuterio derivative (II). These rigid molecules constrain amide groups to nonplanar geometries with twisted pyramidal arrangements of bonds to amide nitrogen atoms. We have collected a full range vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra including signals of C-H and C-D stretching vibrations. We report normal-mode analysis and a comparison of calculated to experimental VCD and ROA. The data provide band-to-band assignment and offer a possibility to evaluate roles of constrained nonplanar tertiary amide groups and rigid chiral skeletons. Nonplanarity shows as single-signed VCD and ROA amide I signals, prevailing the couplets expected to arise from the amide-amide interaction. Amide-amide coupling dominates amide II (mainly C'-N stretching, modified in tertiary amides by the absence of a N-H bond) transitions (strong couplet in VCD, no significant ROA) probably due to the close proximity of amide nitrogen atoms. At lower wavenumbers, ROA spectra exhibit another likely manifestation of amide nonplanarity, showing signals of amide V (δ(oop)(N-C) at ~570 cm(-1)) and amide VI (δ(oop)(C'═O) at ~700 cm(-1) and ~650 cm(-1)) vibrations.

Quantum chemical studies on structural, vibrational, nonlinear optical properties and chemical reactivity of indigo carmine dye

Science.gov (United States)

El-Mansy, M. A. M.

2017-08-01

Structural and vibrational spectroscopic studies were performed on indigo carmine (IC) isomers using FT-IR spectral analysis along with DFT/B3LYP method utilizing Gaussian 09 software. GaussView 5 program has been employed to perform a detailed interpretation of vibrational spectra. Simulation of infrared spectra has led to an excellent overall agreement with the observed spectral patterns. Mulliken population analyses on atomic charges, MEP, HOMO-LUMO, NLO, first order hyperpolarizability and thermodynamic properties have been examined by (DFT/B3LYP) method with the SDD basis set level. Density of state spectra (DOS) were calculated using GaussSum 3 at the same level of theory. Molecular modeling approved that DOS Spectra are the most significant tools for differentiating between two IC isomers so far. Moreover, The IC isomers (cis-isomer) have shown an extended applicability for manufacturing both NLO and photovoltaic devices such as solar cells.

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

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

Science.gov (United States)

Hinde, Robert

2008-03-01

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

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

Generate floor response spectra, Part 2: Response spectra for equipment-structure resonance

International Nuclear Information System (INIS)

Li, Bo; Jiang, Wei; Xie, Wei-Chau; Pandey, Mahesh D.

2015-01-01

Highlights: • The concept of tRS is proposed to deal with tuning of equipment and structures. • Established statistical approaches for estimating tRS corresponding to given GRS. • Derived a new modal combination rule from the theory of random vibration. • Developed efficient and accurate direct method for generating floor response spectra. - Abstract: When generating floor response spectra (FRS) using the direct spectra-to-spectra method developed in the companion paper, probability distribution of t-response spectrum (tRS), which deals with equipment-structure resonance or tuning, corresponding to a specified ground response spectrum (GRS) is required. In this paper, simulation results using a large number of horizontal and vertical ground motions are employed to establish statistical relationships between tRS and GRS. It is observed that the influence of site conditions on horizontal statistical relationships is negligible, whereas the effect of site conditions on vertical statistical relationships cannot be ignored. Considering the influence of site conditions, horizontal statistical relationship suitable for all site conditions and vertical statistical relationships suitable for hard sites and soft sites, respectively, are established. The horizontal and vertical statistical relationships are suitable to estimate tRS for design spectra in USNRC R.G. 1.60 and NUREG/CR-0098, Uniform Hazard Spectra (UHS) in Western North America (WNA), or any GRS falling inside the valid coverage of the statistical relationship. For UHS with significant high frequency spectral accelerations, such as UHS in Central and Eastern North America (CENA), an amplification ratio method is proposed to estimate tRS. Numerical examples demonstrate that the statistical relationships and the amplification ratio method are acceptable to estimate tRS for given GRS and to generate FRS using the direct method in different practical situations.

Generate floor response spectra, Part 2: Response spectra for equipment-structure resonance

Energy Technology Data Exchange (ETDEWEB)

Li, Bo, E-mail: b68li@uwaterloo.ca; Jiang, Wei, E-mail: w46jiang@uwaterloo.ca; Xie, Wei-Chau, E-mail: xie@uwaterloo.ca; Pandey, Mahesh D., E-mail: mdpandey@uwaterloo.ca

2015-11-15

Highlights: • The concept of tRS is proposed to deal with tuning of equipment and structures. • Established statistical approaches for estimating tRS corresponding to given GRS. • Derived a new modal combination rule from the theory of random vibration. • Developed efficient and accurate direct method for generating floor response spectra. - Abstract: When generating floor response spectra (FRS) using the direct spectra-to-spectra method developed in the companion paper, probability distribution of t-response spectrum (tRS), which deals with equipment-structure resonance or tuning, corresponding to a specified ground response spectrum (GRS) is required. In this paper, simulation results using a large number of horizontal and vertical ground motions are employed to establish statistical relationships between tRS and GRS. It is observed that the influence of site conditions on horizontal statistical relationships is negligible, whereas the effect of site conditions on vertical statistical relationships cannot be ignored. Considering the influence of site conditions, horizontal statistical relationship suitable for all site conditions and vertical statistical relationships suitable for hard sites and soft sites, respectively, are established. The horizontal and vertical statistical relationships are suitable to estimate tRS for design spectra in USNRC R.G. 1.60 and NUREG/CR-0098, Uniform Hazard Spectra (UHS) in Western North America (WNA), or any GRS falling inside the valid coverage of the statistical relationship. For UHS with significant high frequency spectral accelerations, such as UHS in Central and Eastern North America (CENA), an amplification ratio method is proposed to estimate tRS. Numerical examples demonstrate that the statistical relationships and the amplification ratio method are acceptable to estimate tRS for given GRS and to generate FRS using the direct method in different practical situations.

Vibrational spectroscopic study and NBO analysis on tranexamic acid using DFT method

Science.gov (United States)

Muthu, S.; Prabhakaran, A.

2014-08-01

In this work, we reported the vibrational spectra of tranexamic acid (TA) by experimental and quantum chemical calculation. The solid phase FT-Raman and FT-IR spectra of the title compound were recorded in the region 4000 cm-1 to 100 cm-1 and 4000 cm-1 to 400 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of TA in the ground state have been calculated by using density functional theory (DFT) B3LYP method with standard 6-31G(d,p) basis set. The scaled theoretical wavenumber showed very good agreement with the experimental values. The vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that ED in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electrostatic potential mapped onto an isodensity surface has been obtained. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase.

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

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

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…

ExoCross: Spectra from molecular line lists

Science.gov (United States)

Yurchenko, Sergei N.; Al-Refaie, Ahmed; Tennyson, Jonathan

2018-03-01

ExoCross generates spectra and thermodynamic properties from molecular line lists in ExoMol, HITRAN, or several other formats. The code is parallelized and also shows a high degree of vectorization; it works with line profiles such as Doppler, Lorentzian and Voigt and supports several broadening schemes. ExoCross is also capable of working with the recently proposed method of super-lines. It supports calculations of lifetimes, cooling functions, specific heats and other properties. ExoCross converts between different formats, such as HITRAN, ExoMol and Phoenix, and simulates non-LTE spectra using a simple two-temperature approach. Different electronic, vibronic or vibrational bands can be simulated separately using an efficient filtering scheme based on the quantum numbers.

FT-Raman and FTIR spectra of photoactive aminobenzazole derivatives in the solid state: A combined experimental and theoretical study

Energy Technology Data Exchange (ETDEWEB)

Alves, Rodrigo Martins [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil); Rodembusch, Fabiano Severo [Universidade Federal do Rio Grande do Sul, Grupo de Pesquisa em Fotoquímica Orgânica Aplicada, Av. Bento Gonçalves 9500, CEP 91501-970 Porto Alegre, RS (Brazil); Habis, Charles [Northern Virginia Community College, Manassas, VA (United States); Moreira, Eduardo Ceretta, E-mail: eduardomoreira@unipampa.edu.br [Universidade Federal do Pampa, Campus Bagé, Grupo de Pesquisa em Espectroscopia de Materiais Fotônicos, 96400-970 Bagé, RS (Brazil)

2014-12-15

This study reports the experimental investigation of two photoactive aminobenzazole derivatives in the solid state by FT-Raman and Infrared Spectroscopies (FTIR) and its comparison with theoretical models. The optimized molecular structure, vibrational frequencies, and corresponding vibrational assignments of these compounds have been investigated experimentally and theoretically using Spanish Initiative for Electronic Simulations with Thousands of Atoms (SIESTA) and Gaussian03 Software Package. The FT-Raman and FTIR spectra were acquired with high resolution and emission frequencies identified by simulating the vibrational modes. The most intense peak observed in the FT-Raman spectra is the in-plane deformation vibrational of O–H bond that could be related to the vibrational region responsible for the stabilization of the enol conformer in the ground state which undergoes ESIPT to form a keto tautomer in the excited state. Additionally, the position of the amino group played an important role on the vibrational characteristics of the studied compounds. Also, the simulations proved to be a good approach in undertaking the FTIR and FT-Raman experiments. The use of graphic correlations helps us to determine the method and basis that best fit the experimental results. - Highlights: • Structural and vibrational properties of two aminobenzazoles were reported. • Comparison between experimental techniques and theoretical models. • The position of the amino group played an important role on the vibrational characteristics of the studied compounds.

Data interpolation for vibration diagnostics using two-variable correlations

International Nuclear Information System (INIS)

Branagan, L.

1991-01-01

This paper reports that effective machinery vibration diagnostics require a clear differentiation between normal vibration changes caused by plant process conditions and those caused by degradation. The normal relationship between vibration and a process parameter can be quantified by developing the appropriate correlation. The differences in data acquisition requirements between dynamic signals (vibration spectra) and static signals (pressure, temperature, etc.) result in asynchronous data acquisition; the development of any correlation must then be based on some form of interpolated data. This interpolation can reproduce or distort the original measured quantity depending on the characteristics of the data and the interpolation technique. Relevant data characteristics, such as acquisition times, collection cycle times, compression method, storage rate, and the slew rate of the measured variable, are dependent both on the data handling and on the measured variable. Linear and staircase interpolation, along with the use of clustering and filtering, provide the necessary options to develop accurate correlations. The examples illustrate the appropriate application of these options

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

Science.gov (United States)

Sakurai, Atsunori; Tanimura, Yoshitaka

2011-04-28

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

Vibronic effects and destruction of exciton coherence in optical spectra of J-aggregates: A variational polaron transformation approach

Energy Technology Data Exchange (ETDEWEB)

Bloemsma, E.A.; Silvis, M.H.; Stradomska, A.; Knoester, J., E-mail: j.knoester@rug.nl

2016-12-20

Using a symmetry adapted polaron transformation of the Holstein Hamiltonian, we study the interplay of electronic excitation-vibration couplings, resonance excitation transfer interactions, and temperature in the linear absorption spectra of molecular J-aggregates. Semi-analytical expressions for the spectra are derived and compared with results obtained from direct numerical diagonalization of the Hamiltonian in the two-particle basis set representation. At zero temperature, we show that our polaron transformation reproduces both the collective (exciton) and single-molecule (vibrational) optical response associated with the appropriate standard perturbation limits. Specifically, for the molecular dimer excellent agreement with the spectra from the two-particle approach for the entire range of model parameters is obtained. This is in marked contrast to commonly used polaron transformations. Upon increasing the temperature, the spectra show a transition from the collective to the individual molecular features, which results from the thermal destruction of the exciton coherence.

Advanced Engine Health Management Applications of the SSME Real-Time Vibration Monitoring System

Science.gov (United States)

Fiorucci, Tony R.; Lakin, David R., II; Reynolds, Tracy D.; Turner, James E. (Technical Monitor)

2000-01-01

The Real Time Vibration Monitoring System (RTVMS) is a 32-channel high speed vibration data acquisition and processing system developed at Marshall Space Flight Center (MSFC). It Delivers sample rates as high as 51,200 samples/second per channel and performs Fast Fourier Transform (FFT) processing via on-board digital signal processing (DSP) chips in a real-time format. Advanced engine health assessment is achieved by utilizing the vibration spectra to provide accurate sensor validation and enhanced engine vibration redlines. Discrete spectral signatures (such as synchronous) that are indicators of imminent failure can be assessed and utilized to mitigate catastrophic engine failures- a first in rocket engine health assessment. This paper is presented in viewgraph form.

N-propyl nitrate vibrational spectrum analysis using DFT B3LYP quantum-chemical method

Science.gov (United States)

Shaikhullina, R. M.; Hrapkovsky, G. M.; Shaikhullina, M. M.

2018-05-01

Calculation of a molecular structure, conformation and related vibrational spectra of the n- propyl nitrate C3H7NO3 was carried out by means of density functional theory (DFT) by employing the Gaussian 03 package. The molecular geometries were fully optimized by using the Becker's three-parameter hybrid exchange functional combined with the Lee–Yang–Parr correlation functional (B3LYP) and using the 6-31G(d) basis set. By scanning the dihedral angles around C-O and C-C bonds, five energetically most favorable conformers of n-propyl nitrate - TG, TT, GT, GG and G´G forms were found. Vibrational spectra of the most energetically favorable conformers were calculated. The comparative analysis of calculated and experimental spectra is carried out, the spectral features of the conformational state of n-propyl nitrate and the spectral effects of formation of intramolecular hydrogen bonds are established.

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.

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.

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

Wind Turbine Bearing Diagnostics Based on Vibration Monitoring

Science.gov (United States)

Kadhim, H. T.; Mahmood, F. H.; Resen, A. K.

2018-05-01

Reliability maintenance can be considered as an accurate condition monitoring system which increasing beneficial and decreasing the cost production of wind energy. Supporting low friction of wind turbine rotating shaft is the main task of rolling element bearing and it is the main part that suffers from failure. The rolling failures elements have an economic impact and may lead to malfunctions and catastrophic failures. This paper concentrates on the vibration monitoring as a Non-Destructive Technique for assessing and demonstrates the feasibility of vibration monitoring for small wind turbine bearing defects based on LabVIEW software. Many bearings defects were created, such as inner race defect, outer race defect, and ball spin defect. The spectra data were recorded and compared with the theoretical results. The accelerometer with 4331 NI USB DAQ was utilized to acquiring, analyzed, and recorded. The experimental results were showed the vibration technique is suitable for diagnostic the defects that will be occurred in the small wind turbine bearings and developing a fault in the bearing which leads to increasing the vibration amplitude or peaks in the spectrum.

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

Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

Energy Technology Data Exchange (ETDEWEB)

DeBlase, Andrew F.; Wolke, Conrad T.; Johnson, Mark A., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Weddle, Gary H. [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Department of Chemistry, Fairfield University, 1073 North Benson Road, Fairfield, Connecticut 06824 (United States); Archer, Kaye A.; Jordan, Kenneth D., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260 (United States); Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677 (United States)

2015-10-14

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

Fourier transform infrared emission spectra of MnH and MnD

Science.gov (United States)

Gordon, Iouli E.; Appadoo, Dominique R. T.; Shayesteh, Alireza; Walker, Kaley A.; Bernath, Peter F.

2005-01-01

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7Σ + electronic state. The vibration-rotation bands from v = 1 → 0 to v = 3 → 2 for MnH and from v = 1 → 0 to v = 4 → 3 for MnD were recorded at an instrumental resolution of 0.0085 cm -1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant ( ωe) for MnH was found to be 1546.84518(65) cm -1, the equilibrium rotational constant ( Be) is 5.6856789(103) cm -1 and the eqilibrium bond distance ( re) was determined to be 1.7308601(47) Å.

[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).

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.

Raman spectra of long chain hydrocarbons: anharmonic calculations, experiment and implications for imaging of biomembranes.

Science.gov (United States)

Šebek, Jiří; Pele, Liat; Potma, Eric O; Gerber, R Benny

2011-07-28

First-principles anharmonic vibrational calculations are carried out for the Raman spectrum of the C-H stretching bands in dodecane, and for the C-D bands in the deuterated molecule. The calculations use the Vibrational Self-Consistent Field (VSCF) algorithm. The results are compared with liquid-state experiments, after smoothing the isolated-molecule sharp-line computed spectra. Very good agreement between the computed and experimental results is found for the two systems. The combined theoretical and experimental results provide insights into the spectrum, elucidating the roles of symmetric and asymmetric CH(3) and CH(2) hydrogenic stretches. This is expected to be very useful for the interpretation of spectra of long-chain hydrocarbons. The results show that anharmonic effects on the spectrum are large. On the other hand, vibrational degeneracy effects seem to be rather modest at the resolution of the experiments. The degeneracy effects may have more pronounced manifestations in higher-resolution experiments. The results show that first-principles anharmonic vibrational calculations for hydrocarbons are feasible, in good agreement with experiment, opening the way for applications to many similar systems. The results may be useful for the analysis of CARS imaging of lipids, for which dodecane is a representative molecule. It is suggested that first-principles vibrational calculations may be useful also for CARS imaging of other systems. This journal is © the Owner Societies 2011

Chains of benzenes with lithium-atom adsorption: Vibrations and spontaneous symmetry breaking

OpenAIRE

Ortiz, Yenni P.; Stegmann, Thomas; Klein, Douglas J.; Seligman, Thomas H.

2016-01-01

We study effects of different configurations of adsorbates on the vibrational modes as well as symmetries of polyacenes and poly-p-phenylenes focusing on lithium atom adsorption. We found that the spectra of the vibrational modes distinguish the different configurations. For more regular adsorption schemes the lowest states are bending and torsion modes of the skeleton, which are essentially followed by the adsorbate. On poly-p-phenylenes we found that lithium adsorption reduces and often eli...

Experimental and computational study on molecular structure and vibrational analysis of a modified biomolecule: 5-Bromo-2'-deoxyuridine

Science.gov (United States)

Çırak, Çağrı; Sert, Yusuf; Ucun, Fatih

In the present study, the experimental and theoretical vibrational spectra of 5-bromo-2'-deoxyuridine were investigated. The experimental FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths and bond angles) were calculated using ab initio Hartree Fock (HF) and density functional B3LYP method with 6-31G(d), 6-31G(d,p), 6-311++G(d) and 6-311++G(d,p) basis sets by Gaussian program, for the first time. The assignments of vibrational frequencies were performed by potential energy distribution by using VEDA 4 program. The optimized geometric parameters and theoretical vibrational frequencies are compared with the corresponding experimental data and they were seen to be in a good agreement with the each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

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)

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

International Nuclear Information System (INIS)

Lauhon, L. J.; Ho, W.

2001-01-01

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

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.

Two-dimensional spectra of electron collisions with acrylonitrile and methacrylonitrile reveal nuclear dynamics

Energy Technology Data Exchange (ETDEWEB)

Regeta, K., E-mail: khrystyna.regeta@unifr.ch; Allan, M., E-mail: michael.allan@unifr.ch [Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg (Switzerland)

2015-05-14

Detailed experimental information on the motion of a nuclear packet on a complex (resonant) anion potential surface is obtained by measuring 2-dimensional (2D) electron energy loss spectra. The cross section is plotted as a function of incident electron energy, which determines which resonant anion state is populated, i.e., along which normal coordinate the wave packet is launched, and of the electron energy loss, which reveals into which final states each specific resonant state decays. The 2D spectra are presented for acrylonitrile and methacrylonitrile, at the incident energy range 0.095-1.0 eV, where the incoming electron is temporarily captured in the lowest π{sup ∗} orbital. The 2D spectra reveal selectivity patterns with respect to which vibrations are excited in the attachment and de-excited in the detachment. Further insight is gained by recording 1D spectra measured along horizontal, vertical, and diagonal cuts of the 2D spectrum. The methyl group in methacrylonitrile increases the resonance width 7 times. This converts the sharp resonances of acrylonitrile into boomerang structures but preserves the essence of the selectivity patterns. Selectivity of vibrational excitation by higher-lying shape resonances up to 8 eV is also reported.

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.

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)

Influence of light-induced conical intersection on the photodissociation dynamics of D2(+) starting from individual vibrational levels.

Science.gov (United States)

Halász, Gábor J; Csehi, András; Vibók, Ágnes; Cederbaum, Lorenz S

2014-12-26

Previous works have shown that dressing of diatomic molecules by standing or by running laser waves gives rise to the appearance of so-called light-induced conical intersections (LICIs). Because of the strong nonadiabatic couplings, the existence of such LICIs may significantly change the dynamical properties of a molecular system. In our former paper (J. Phys. Chem. A 2013, 117, 8528), the photodissociation dynamics of the D(2)(+) molecule were studied in the LICI framework starting the initial vibrational nuclear wave packet from the superposition of all the vibrational states initially produced by ionizing D(2). The present work complements our previous investigation by letting the initial nuclear wave packets start from different individual vibrational levels of D(2)(+), in particular, above the energy of the LICI. The kinetic energy release spectra, the total dissociation probabilities, and the angular distributions of the photofragments are calculated and discussed. An interesting phenomenon has been found in the spectra of the photofragments. Applying the light-induced adiabatic picture supported by LICI, explanations are given for the unexpected structure of the spectra.

Cross sections for the vibrational excitation of the H2 X 1Σ+g(v) levels generated by electron collisional excitation of the higher singlet states

International Nuclear Information System (INIS)

Hiskes, J.R.

1991-01-01

The excitation cross sections, σ(v,v double-prime), for an H 2 molecule initially in any one of the 15 vibrational levels, v belonging to the ground electronic state and excited to a final vibrational level, v double-prime are evaluated for direct excitations via all members of the excited electronic singlet spectrum. Account is taken of predissociation, autoionization, and radiative decay of the excited electronic spectrum that leads to a final population distribution for the ground electronic state, X 1 Σ + g (v double-prime). For v=0, account is taken explicitly of transitions via the B, C, B', and D electronic states in evaluating the cross sections. The additional contribution of excitations via all Rydberg states lying above the D state enhances these cross sections by approximately 10%. For v>0, cross sections are evaluated taking explicit account of transitions through the B and C states; higher singlet excitations enhance these values by 25%. The choice of the reference total cross sections remains a subjective one, causing the values calculated here to have a possible uncertainty of +20% -30% . For excitations occurring within a hydrogen discharge, collisional excitation-ionization events among the intermediate singlet states will effectively quench the v, v double-prime excitation process for discharge densities in excess of the range 10 15 --10 16 electrons/cm -3

Task-specific recruitment of motor units for vibration damping.

Science.gov (United States)

Wakeling, James M; Liphardt, Anna-Maria

2006-01-01

Vibrations occur within the soft tissues of the lower extremities due to the heel-strike impact during walking. Increases in muscle activity in the lower extremities result in increased damping to reduce this vibration. The myoelectric intensity spectra were compared using principal component analysis from the tibialis anterior and lateral gastrocnemius of 40 subjects walking with different shoe conditions. The soft insert condition resulted in a significant, simultaneous increase in muscle activity with a shift to higher myoelectric frequencies in the period 0-60 ms after heel-strike which is the period when the greater vibration damping occurred. These increases in myoelectric frequency match the spectral patterns which indicate increases in recruitment of faster motor units. It is concluded that fast motor units are recruited during the task of damping the soft-tissue resonance that occurs following heel-strike.

State-of-the-art of development of floor spectra

International Nuclear Information System (INIS)

Singh, M.P.

1984-01-01

Floor spectra are used as seismic inputs for the design and qualification of subsystems and equipment. Until very recently, the time history analyses with single acceleration time history as input were very commonly used. However, this approach has been observed to give nonunique floor spectrum curves. Thus, as alternatives several direct approaches have been developed. The approaches which are based on the random vibration principles but employ response spectra directly have more rational appeal. Several such approaches are available. Four different approaches, employing the mode displacement and mode acceleration formulations, covering the proportionally as well as nonproportionally damped structures, are presented. The mode displacement formulations are most commonly used, although the mode acceleration formulations seem to be the better alternatives, both for the proportionally and nonproportionally damped structures. The need for the development of other forms of floor response spectra such as the relative velocity and relative acceleration spectra is also identified

The use of UV, FT-IR and Raman spectra for the identification of the newest penem analogs: solutions based on mathematic procedure and the density functional theory.

Science.gov (United States)

Cielecka-Piontek, J; Lewandowska, K; Barszcz, B; Paczkowska, M

2013-02-15

The application of ultraviolet, FT-IR and Raman spectra was proposed for identification studies of the newest penem analogs (doripenem, biapenem and faropenem). An identification of the newest penem analogs based on their separation from related substances was achieved after the application of first derivative of direct spectra in ultraviolet which permitted elimination of overlapping effects. A combination of experimental and theoretical studies was performed for analyzing the structure and vibrational spectra (FT-IR and Raman spectra) of doripenem, biapenem and faropenem. The calculations were conducted using the density functional theory with the B3LYP hybrid functional and 6-31G(d,p) basis set. The confirmation of the applicability of the DFT methodology for interpretation of vibrational IR and Raman spectra of the newest penem analogs contributed to determination of changes of vibrations in the area of the most labile bonds. By employing the theoretical approach it was possible to eliminate necessity of using reference standards which - considering the instability of penem analogs - require that correction coefficients are factored in. Copyright © 2012 Elsevier B.V. All rights reserved.

[Raman, FTIR spectra and normal mode analysis of acetanilide].

Science.gov (United States)

Liang, Hui-Qin; Tao, Ya-Ping; Han, Li-Gang; Han, Yun-Xia; Mo, Yu-Jun

2012-10-01

The Raman and FTIR spectra of acetanilide (ACN) were measured experimentally in the regions of 3 500-50 and 3 500-600 cm(-1) respectively. The equilibrium geometry and vibration frequencies of ACN were calculated based on density functional theory (DFT) method (B3LYP/6-311G(d, p)). The results showed that the theoretical calculation of molecular structure parameters are in good agreement with previous report and better than the ones calculated based on 6-31G(d), and the calculated frequencies agree well with the experimental ones. Potential energy distribution of each frequency was worked out by normal mode analysis, and based on this, a detailed and accurate vibration frequency assignment of ACN was obtained.

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

Science.gov (United States)

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

2013-11-01

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

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.

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.

The Mossbauer spectra of carbon nanotubes synthesize using ferrite catalyst

International Nuclear Information System (INIS)

Zhang Haiyan; Lin Jiapeng; Peng Zuxiong; Zeng Guoxun; Pang Jinshan; Chen Yiming

2009-01-01

The ferrite powder with honeycombed structure obtained by chemical combustion was used as catalyst to synthesize multi-walled carbon nanotubes by chemical vapor deposition. The magnetic components and characters of the the carbon nanotubes synthesized were investigated by X-ray diffraction (XRD), Mossbauer spectra and vibrating-sample magnetometer (VSM). The ferric components of the carbon nanotubes samples can be identified by Mossbauer spectra. The Mossbauer spectra of carbon nanotubes sample after purification contains two ferromagnetic sextet components corresponding to α-Fe species and Fe 3 C (cementite) species. While the Mossbauer spectra of the carbon nanotubes sample before purification contains three ferromagnetic sextet components corresponding to α-Fe species, Fe 3 C species and γ-Fe 2 O 3 . The saturation magnetization intensity Ms of carbon nanotubes sample after purification is decreased from 46.61 to 2.94 emu/g, but the coercive force increasd and reached 328Oe.

MOLECULAR STRUCTURE AND VIBRATIONAL FREQUENCIES OF

Directory of Open Access Journals (Sweden)

Fatih UCUN

2009-02-01

Full Text Available Abstract: The molecular structure, vibrational frequencies and the corresponding assignments of N-aminophthalimide (NAPH in the ground state have been calculated using the Hartree-Fock (HF and density functional methods (B3LYP with 6-31G (d, p basis set. The calculations were utilized in the CS symmetry of NAPH. The obtained vibrational frequencies and optimized geometric parameters (bond lengths and bond angles were seen to be in good agreement with the experimental data. The comparison of the observed and calculated results showed that B3LYP is superior to the scaled HF method. Theoretical infrared intensities and Raman activities were also reported. Key words: N-aminophthalimide; vibrations; IR spectra; Raman spectra; HF; DFT N-AMİNOFİTALOMİD'İN MOLEKÜLER YAPISI VE TİTREŞİM FREKANSLARI Özet: Temel haldeki N-aminofitalamidin (NAPH moleküler yapısı, titreşim frekansları ve uygun mod tanımlamaları, 6-31 G (d, p temel setli Hartree-Fock (HF ve yoğunluk fonksiyonu metodları (B3LYP kullanılarak hesaplandı. Hesaplamalar, NAPH'ın CS simetrisine uyarlandı. Elde edilen titreşim frekansları ve optimize geometrik parametreleri (bağ uzunlukları ve bağ açıları, deneysel değerlerle iyi bir uyum içinde olduğu görüldü. Deneysel ve teorik sonuçların karşılaştırılması, B3LYP'nin HF metodundan daha üstün olduğunu gösterdi. Ayrıca teorik infrared şiddetleri ve Raman aktiviteleri verildi. Anahtar Kelimeler: N-aminofitalamidin; titreşimler; IR spektrumu; Raman Spektrumu; HF; DFT

Quantum Calculation for Musk Molecules Infrared Spectra towards the Understanding of Odor

Directory of Open Access Journals (Sweden)

Elaine Rose Maia

2014-01-01

Full Text Available It is not clear so far how humans can recognize odor. One of the theories regarding structure-odor relationship is vibrational theory, which claims that odors can be recognized by their modes of vibration. In this sense, this paper brings a novel comparison made between musky and nonmusky molecules, as to check the existence of correlation between their modes on the infrared spectra and odor. For this purpose, sixteen musky odorants were chosen, as well as seven other molecules that are structurally similar to them, but with no musk odor. All of them were submitted to solid theoretical methodology (using molecular mechanics/molecular dynamics and Neglect of Diatomic Differential Overlap Austin Model 1 methods to optimize geometries as to achieve density functional theory spectra information, with both Gradient Corrected Functional Perdew-Wang generalized-gradient approximation (GGA/PW91 and hybrid Becke, three-parameter, Lee-Yang-Parr (B3LYP functional. For a proper analysis over spectral data, a mathematical method was designed, generating weighted averages for theoretical frequencies and computing deviations from these averages. It was then devised that musky odorants satisfied demands of the vibrational theory, while nonmusk compounds belonging either to nitro group or to acyclic group failed to fulfill the same criteria.

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.

Measurements of vibrational excitation of N2, CO, and NO by low energy proton impact

International Nuclear Information System (INIS)

Krutein, J.; Linder, F.

1979-01-01

Differential scattering experiments are reported for proton impact on N 2 , CO, and NO in the energy range E/sub lab/=30--80 eV. The measurements include the range of very small scattering angles around 0 0 as well as the rainbow region. The vibrationally resolved energy-loss spectra show a relatively low vibrational inelasticity for all three systems. Differential cross sections, transition probabilities, and the mean vibrational energy transfer are presented. Rotational excitation is indicated by the broadening of the energy-loss peaks which is most significant for H + --NO. The small-angle scattering data for vibrational excitation in CO show good agreement with the impact parameter theory using the known long-range interactions for this system

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

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

FT-IR spectra of the anti-HIV nucleoside analogue d4T (Stavudine). Solid state simulation by DFT methods and scaling by different procedures

Science.gov (United States)

Alcolea Palafox, M.; Kattan, D.; Afseth, N. K.

2018-04-01

A theoretical and experimental vibrational study of the anti-HIV d4T (stavudine or Zerit) nucleoside analogue was carried out. The predicted spectra in the three most stable conformers in the biological active anti-form of the isolated state were compared. Comparison of the conformers with those of the natural nucleoside thymidine was carried out. The calculated spectra were scaled by using different scaling procedures and three DFT methods. The TLSE procedure leads to the lowest error and is thus recommended for scaling. With the population of these conformers the IR gas-phase spectra were predicted. The crystal unit cell of the different polymorphism forms of d4T were simulated through dimer forms by using DFT methods. The scaled spectra of these dimer forms were compared. The FT-IR spectrum was recorded in the solid state in the 400-4000 cm-1 range. The respective vibrational bands were analyzed and assigned to different normal modes of vibration by comparison with the scaled vibrational values of the different dimer forms. Through this comparison, the polymorphous form of the solid state sample was identified. The study indicates that d4T exist only in the ketonic form in the solid state. The results obtained were in agreement with those determined in related anti-HIV nucleoside analogues.

Determination of vibration amplitudes and neutron-mechanical scale factors in the PWR nuclear power plant

International Nuclear Information System (INIS)

Kostic, Lj.; Heidemann, P.; Runkel, J.

1997-01-01

Displacements of vibrating reactor components which can not be measured by other means during normal reactor operation can be determined through the scale factors from the neutron spectra of signals measured by the standard in-core neutron instrumentation. Neutron-mechanical scale factors are determined for the vibrations of fuel assemblies and reactor pressure vessel/core barrel system using the signals of in-core neutron detectors and accelerometers. (author)

Studies of the Raman Spectra of Cyclic and Acyclic Molecules: Combination and Prediction Spectrum Methods

Energy Technology Data Exchange (ETDEWEB)

Kim, Taijin; Assary, Rajeev S.; Marshall, Christopher L.; Gosztola, David J.; Curtiss, Larry A.; Stair, Peter C.

2012-04-02

A combination of Raman spectroscopy and density functional methods was employed to investigate the spectral features of selected molecules: furfural, 5-hydroxymethyl furfural (HMF), methanol, acetone, acetic acid, and levulinic acid. The computed spectra and measured spectra are in excellent agreement, consistent with previous studies. Using the combination and prediction spectrum method (CPSM), we were able to predict the important spectral features of two platform chemicals, HMF and levulinic acid.The results have shown that CPSM is a useful alternative method for predicting vibrational spectra of complex molecules in the biomass transformation process.

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

International Nuclear Information System (INIS)

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

2004-01-01

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

The sub-bandgap energy loss satellites in the RIXS spectra of beryllium compounds

International Nuclear Information System (INIS)

Kuusik, I.; Kaeaembre, T.; Kooser, K.; Pustovarov, V.; Ivanov, V.; Kukk, E.; Kikas, A.

2011-01-01

Research highlights: → Be 1s RIXS spectra have been measured in Be containing crystals phenakite and chrysoberyl. → A strong energy loss sideband to the elastic scattering peak similar to BeO is found in both minerals. → Additionally the Si 2p RIXS spectra of phenakite also show a strong energy loss sideband to the elastic scattering peak. → The energy loss shoulder appears to result from lattice relaxation in the absorption site. - Abstract: Resonant X-ray inelastic scattering spectra have been measured in BeO, phenakite (Be 2 SiO 4 ) and chrysoberyl (BeAl 2 O 4 ) with the excitation energy near the beryllium K edge. The RIXS spectra excited in the vicinity of the Be 1s core resonance show two principal features: the scattering on a valence excitation (which at higher excitation energies verges into the characteristic K α emission), and a remarkably strong energy loss sideband to the elastic scattering peak. The energy loss shoulder appears to result from lattice relaxation in the absorption site. The comparison of the RIXS spectra of phenakite, chrysoberyl and BeO shows that the strength of the low energy sideband differs greatly; it is strongest in BeO and weakest in phenakite. The Si 2p RIXS spectra of phenakite also display a similar strong sub-bandgap energy loss tail. To gain further insight to this process, transitions in a system with a single vibrational mode have been modelled. The phonon relaxation has been simulated empirically by 'smearing' the photoabsortion-populated vibrational levels with lower levels. This simple model is able to qualitatively explain this wide energy loss shoulder.

The sub-bandgap energy loss satellites in the RIXS spectra of beryllium compounds

Energy Technology Data Exchange (ETDEWEB)

Kuusik, I., E-mail: ivar@fi.tartu.ee [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia); Kaeaembre, T. [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia); Kooser, K. [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia); Department of Physics and Astronomy, University of Turku, Turku (Finland); Pustovarov, V.; Ivanov, V. [Ural State Technical University-UPI, Yekaterinburg (Russian Federation); Kukk, E. [Department of Physics and Astronomy, University of Turku, Turku (Finland); Kikas, A. [Institute of Physics, University of Tartu, Riia 142, 51014 Tartu (Estonia)

2011-07-15

Research highlights: {yields} Be 1s RIXS spectra have been measured in Be containing crystals phenakite and chrysoberyl. {yields} A strong energy loss sideband to the elastic scattering peak similar to BeO is found in both minerals. {yields} Additionally the Si 2p RIXS spectra of phenakite also show a strong energy loss sideband to the elastic scattering peak. {yields} The energy loss shoulder appears to result from lattice relaxation in the absorption site. - Abstract: Resonant X-ray inelastic scattering spectra have been measured in BeO, phenakite (Be{sub 2}SiO{sub 4}) and chrysoberyl (BeAl{sub 2}O{sub 4}) with the excitation energy near the beryllium K edge. The RIXS spectra excited in the vicinity of the Be 1s core resonance show two principal features: the scattering on a valence excitation (which at higher excitation energies verges into the characteristic K{sub {alpha}} emission), and a remarkably strong energy loss sideband to the elastic scattering peak. The energy loss shoulder appears to result from lattice relaxation in the absorption site. The comparison of the RIXS spectra of phenakite, chrysoberyl and BeO shows that the strength of the low energy sideband differs greatly; it is strongest in BeO and weakest in phenakite. The Si 2p RIXS spectra of phenakite also display a similar strong sub-bandgap energy loss tail. To gain further insight to this process, transitions in a system with a single vibrational mode have been modelled. The phonon relaxation has been simulated empirically by 'smearing' the photoabsortion-populated vibrational levels with lower levels. This simple model is able to qualitatively explain this wide energy loss shoulder.

Density functional theory, comparative vibrational spectroscopic studies, highest occupied molecular orbital and lowest unoccupied molecular orbital analysis of Linezolid

Science.gov (United States)

Rajalakshmi, K.; Gunasekaran, S.; Kumaresan, S.

2015-06-01

The Fourier transform infrared spectra and Fourier transform Raman spectra of Linezolid have been recorded in the regions 4,000-400 and 4,000-100 cm-1, respectively. Utilizing the observed Fourier transform infrared spectra and Fourier transform Raman spectra data, a complete vibrational assignment and analysis of the fundamental modes of the compound have been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, have been calculated by density functional theory with 6-31G(d,p), 6-311G(d,p) and M06-2X/6-31G(d,p) levels. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of Linezolid is reported. Mulliken's net charges have also been calculated. Ultraviolet-visible spectrum of the title molecule has also been calculated using time-dependent density functional method. Besides, molecular electrostatic potential, highest occupied molecular orbital and lowest unoccupied molecular orbital analysis and several thermodynamic properties have been performed by the density functional theoretical method.

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.

Vibrational analysis of 4-chloro-3-nitrobenzonitrile by quantum chemical calculations

Science.gov (United States)

Sert, Yusuf; Çırak, Çağrı; Ucun, Fatih

2013-04-01

In the present study, the experimental and theoretical harmonic and anharmonic vibrational frequencies of 4-chloro-3-nitrobenzonitrile were investigated. The experimental FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths and bond angles) were calculated using ab initio Hartree Fock (HF), density functional B3LYP and M06-2X methods with 6-311++G(d,p) basis set by Gaussian 09 W program, for the first time. 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 data, and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

The Raman and vibronic activity of intermolecular vibrations in aromatic-containing complexes and clusters

International Nuclear Information System (INIS)

Maxton, P.M.; Schaeffer, M.W.; Ohline, S.M.; Kim, W.; Venturo, V.A.; Felker, P.M.

1994-01-01

Theoretical and experimental results pertaining to the excitation of intermolecular vibrations in the Raman and vibronic spectra of aromatic-containing, weakly bound complexes and clusters are reported. The theoretical analysis of intermolecular Raman activity is based on the assumption that the polarizability tensor of a weakly bound species is given by the sum of the polarizability tensors of its constituent monomers. The analysis shows that the van der Waals bending fundamentals in aromatic--rare gas complexes may be expected to be strongly Raman active. More generally, it predicts strong Raman activity for intermolecular vibrations that involve the libration or internal rotation of monomer moieties having appreciable permanent polarizability anisotropies. The vibronic activity of intermolecular vibrations in aromatic-rare gas complexes is analyzed under the assumption that every vibronic band gains its strength from an aromatic-localized transition. It is found that intermolecular vibrational excitations can accompany aromatic-localized vibronic excitations by the usual Franck--Condon mechanism or by a mechanism dependent on the librational amplitude of the aromatic moiety during the course of the pertinent intermolecular vibration. The latter mechanism can impart appreciable intensity to bands that are forbidden by rigid-molecule symmetry selection rules. The applicability of such rules is therefore called into question. Finally, experimental spectra of intermolecular transitions, obtained by mass-selective, ionization-detected stimulated Raman spectroscopies, are reported for benzene--X (X=Ar, --Ar 2 , N 2 , HCl, CO 2 , and --fluorene), fluorobenzene--Ar and --Kr, aniline--Ar, and fluorene--Ar and --Ar 2 . The results support the conclusions of the theoretical analyses and provide further evidence for the value of Raman methods in characterizing intermolecular vibrational level structures

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-01

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

High resolution emission Fourier transform infrared spectra of the 4p-5s and 5p-6s bands of ArH.

Science.gov (United States)

Baskakov, O I; Civis, S; Kawaguchi, K

2005-03-15

In the 2500-8500 cm(-1) region several strong emission bands of (40)ArH were observed by Fourier transform spectroscopy through a dc glow discharge in a mixture of argon and hydrogen. Rotational-electronic transitions of the two previously unstudied 4p-5s and 5p-6s,v = 0-0, bands of (40)ArH were measured and assigned in the 6060 and 3770 cm(-1) regions, respectively. A simultaneous fit of the emission transitions of the 4p-5s and 5p-6s bands and an extended set of transitions of the 6s-4p band observed by Dabrowski, Tokaryk, and Watson [J. Mol. Spectrosc. 189, 95 (1998)] and remeasured in the present work yielded consistent values of the spectroscopic parameters of the electronic states under investigation. In the branch of the 4p-5s band with transitions of type (Q)Q(f(3)e) we observed a narrowing in the linewidths with increasing rotational quantum number N. The rotational dependence of the linewidth is caused by predissociation of the 5s state by the repulsive ground 4s state through homogeneous coupling and changes in overlap integrals of the vibrational wave functions with the rotational level. Analysis was based on the Fermi's golden rule approximation model. In the 4p-5s band region a vibrational sequence ofv(')-v(")=1-1, 2-2, and 3-3 were recorded and a number of transitions belonging to the strongest (Q)Q(f(3)e) form branch of the 1-1 band were analyzed.

Resonant Raman and FTIR spectra of carbon doped GaN

Science.gov (United States)

Ito, S.; Kobayashi, H.; Araki, K.; Suzuki, K.; Sawaki, N.; Yamashita, K.; Honda, Y.; Amano, H.

2015-03-01

Intentionally carbon (C) doped (0 0 0 1)GaN was grown using C2H2 on a sapphire substrate by metalorganic vapor phase epitaxy. Optical spectra of the heavily doped samples were investigated at room temperature. In Raman spectra excited by the 325 nm line of a He-Cd laser, multiple LO phonon scattering signals up to 7th order were observed, and the A1(LO) phonon energy was determined to be 737.5 cm-1 (91.45 meV). In infrared reflectance spectra, on the other hand, a local vibration mode was found at 777.5 cm-1, which is attributed to a Ga-C bond in the GaN matrix suggesting that the C sits on an N site (CN). In spite of the strong suggestion of CN, the samples did not show p-type conduction. Possible origin of the carrier compensation is discussed in relation to the enhancement of defect related yellow luminescence in the photoluminescence spectra.

Translational, rotational, vibrational and electron temperatures of a gliding arc discharge

DEFF Research Database (Denmark)

Zhu, Jiajian; Ehn, Andreas; Gao, Jinlong

2017-01-01

, 0) band was used to simulate the rotational temperature (Tr) of the gliding arc discharge whereas the NO A–X (1, 0) and (0, 1) bands were used to determine its vibrational temperature (Tv). The instantaneous reduced electric field strength E/N was obtained by simultaneously measuring......Translational, rotational, vibrational and electron temperatures of a gliding arc discharge in atmospheric pressure air were experimentally investigated using in situ, non-intrusive optical diagnostic techniques. The gliding arc discharge was driven by a 35 kHz alternating current (AC) power source...... and operated in a glow-type regime. The two-dimensional distribution of the translational temperature (Tt) of the gliding arc discharge was determined using planar laser-induced Rayleigh scattering. The rotational and vibrational temperatures were obtained by simulating the experimental spectra. The OH A–X (0...

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

Science.gov (United States)

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

2016-03-10

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

First international symposium on Flow Induced Noise and Vibration Issues and Aspects

CERN Document Server

Rosa, Sergio; Franco, Francesco; Guyader, Jean-Louis; Hambric, Stephen; Flinovia - Flow Induced Noise and Vibration Issues and Aspects

2015-01-01

Flow induced vibration and noise (FIVN) remains a critical research topic. Even after over 50 years of intensive research, accurate and cost-effective FIVN simulation and measurement techniques remain elusive. This book gathers the latest research from some of the most prominent experts in the field. It describes methods for characterizing wall pressure fluctuations, including subsonic and supersonic turbulent boundary layer flows over smooth and rough surfaces using computational methods like Large Eddy Simulation;
for inferring wall pressure fluctuations using inverse techniques based on panel vibrations or holographic pressure sensor arrays;
for calculating the resulting structural vibrations and radiated sound using traditional finite element methods, as well as advanced methods like Energy Finite Elements;
for using scaling approaches to universally collapse flow-excited vibration and noise spectra; and for computing time histories of structural response, including alternating stresses. This book p...

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

Vibrational modes of deuterium in KD2PO4

International Nuclear Information System (INIS)

Mizoguchi, Kohji; Agui, Akane; Tominaga, Yasunori; Nakai, Yusuke; Ikeda, Susumu.

1993-01-01

In order to study the deuteration effect in hydrogen-bonded compounds such as KH 2 PO 4 , hydrogen and deuterium modes in KH 2 PO 4 and K(D x H 1-x ) 2 PO 4 (x = 95 %) were investigated by means of inelastic neutron-scattering measurements over a wide energy range. By comparing Raman spectra of KH 2 PO 4 and KD 2 PO 4 with neutron-scattering spectra, the vibrational modes of deuterium and those of PO 4 tetrahedrons in the energy range of 30 < ε < 150 meV have been investigated. At least two deuterium modes have been found at 87 meV and 106 meV. (author)

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

International Nuclear Information System (INIS)

Marumori, Toshio; Kuriyama, Atsushi; Sakata, Fumihiko

1980-01-01

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

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

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.

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

Science.gov (United States)

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

2013-06-01

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

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

Theoretical study of IR and photoelectron spectra of small gallium-arsenide clusters

Energy Technology Data Exchange (ETDEWEB)

Pouchan, Claude; Marchal, Rémi; Hayashi, Shinsuke [Université de Pau et des Pays de l' Adour, IPREM/ECP, UMR CNRS 5254 (France)

2015-01-22

Relative stabilities of small Ga{sub n}As{sub m} clusters, as well as their structural electronic and vibrational properties, were computed and analysed using a CCSD(T) reference method since experimental data in this area are sparse or unknown. With the aim of investigating larger clusters, we explored several DFT functionals and basis sets able to mimic the reliable CCSD(T) approach. Among them, the PBE0/SBKJC+sp,d appears as the most efficient to describe the structural and vibrational properties since average differences of about 0.042Å and 5.1cm{sup −1} were obtained for bond lengths and fundamental vibrational frequencies, respectively for the first small clusters [1] of the series found from our GSAM method [2]. As further test, this model is used in order to investigate and revisit an experimental IR spectrum of Ga{sub n}As{sub m} mixture previously published by Li et al. [3]. More complicated is the difficulty which arises in the electronic description due to the presence of numerous low lying electronic states nearly degenerated to correctly describe the electronic structure. The case of Ga{sub 2}As will be discussed and the photoelectron spectra of the Ga{sub 2}As anion reanalyzed on the ground of our calculations [4] comparatively to the experimental spectra obtained by Neumark and co-workers [5].

Marshak Lectureship: Vibrational properties of isolated color centers in diamond

Science.gov (United States)

Alkauskas, Audrius

In this talk we review our recent work on first-principles calculations of vibrational properties of isolated defect spin qubits and single photon emitters in diamond. These properties include local vibrational spectra, luminescence lineshapes, and electron-phonon coupling. They are key in understanding physical mechanisms behind spin-selective optical initialization and read-out, quantum efficiency of single-photon emitters, as well as in the experimental identification of as yet unknown centers. We first present the methodology to calculate and analyze vibrational properties of effectively isolated defect centers. We then apply the methodology to the nitrogen-vacancy and the silicon-vacancy centers in diamond. First-principles calculations yield important new insights about these important defects. Work performed in collaboration with M. W. Doherty, A. Gali, E. Londero, L. Razinkovas, and C. G. Van de Walle. Supported by the Research Council of Lithuania (Grant M-ERA.NET-1/2015).

Vibration phenomena in large scale pressure suppression tests

International Nuclear Information System (INIS)

Aust, E.; Boettcher, G.; Kolb, M.; Sattler, P.; Vollbrandt, J.

1982-01-01

Structure und fluid vibration phenomena (acceleration, strain; pressure, level) were observed during blow-down experiments simulating a LOCA in the GKSS full scale multivent pressure suppression test facility. The paper describes first the source related excitations during the two regimes of condensation oscillation and of chugging, and deals then with the response vibrations of the facility's wetwell. Modal analyses of the wetwell were run using excitation by hammer and by shaker in order to separate phenomena that are particular to the GKSS facility from more general ones, i.e. phenomena specific to the fluid related parameters of blowdown and to the geometry of the vent pipes only. The lowest periodicities at about 12 and 16 Hz stem from the vent acoustics. A frequency of about 36 to 38 Hz prominent during chugging seems to result from the lowest local models of two of the wetwell's walls when coupled by the wetwell pool. Further peaks found during blowdown in the spectra of signals at higher frequencies correspond to global vibration modes of the wetwell. (orig.)

FTIR, FT-Raman, UV-Visible spectra and quantum chemical calculations of allantoin molecule and its hydrogen bonded dimers.

Science.gov (United States)

Alam, Mohammad Jane; Ahmad, Shabbir

2015-02-05

FTIR, FT-Raman and electronic spectra of allantoin molecule are recorded and investigated using DFT and MP2 methods with 6-311++G(d,p) basis set. The molecular structure, anharmonic vibrational spectra, natural atomic charges, non-linear optical properties, etc. have been computed for the ground state of allantoin. The anharmonic vibrational frequencies are calculated using PT2 algorithm (Barone method) as well as VSCF and CC-VSCF methods. These methods yield results that are in remarkable agreement with the experiment. The coupling strengths between pairs of modes are also calculated using coupling integral based on 2MR-QFF approximation. The simulations on allantoin dimers have been also performed at B3LYP/6-311++G(d,p) level of theory to investigate the effect of the intermolecular interactions on the molecular structure and vibrational frequencies of the monomer. Vibrational assignments are made with the great accuracy using PED calculations and animated modes. The combination and overtone bands have been also identified in the FTIR spectrum with the help of anharmonic computations. The electronic spectra are simulated in gas and solution at TD-B3LYP/6-311++G(d,p) level of theory. The important global quantities such as electro-negativity, electronic chemical potential, electrophilicity index, chemical hardness and softness based on HOMO, LUMO energy eigenvalues are also computed. NBO analysis has been performed for monomer and dimers of allantoin at B3LYP/6-311++G(d,p) level of theory. Copyright © 2014 Elsevier B.V. All rights reserved.

Method for the deconvolution of incompletely resolved CARS spectra in chemical dynamics experiments

International Nuclear Information System (INIS)

Anda, A.A.; Phillips, D.L.; Valentini, J.J.

1986-01-01

We describe a method for deconvoluting incompletely resolved CARS spectra to obtain quantum state population distributions. No particular form for the rotational and vibrational state distribution is assumed, the population of each quantum state is treated as an independent quantity. This method of analysis differs from previously developed approaches for the deconvolution of CARS spectra, all of which assume that the population distribution is Boltzmann, and thus are limited to the analysis of CARS spectra taken under conditions of thermal equilibrium. The method of analysis reported here has been developed to deconvolute CARS spectra of photofragments and chemical reaction products obtained in chemical dynamics experiments under nonequilibrium conditions. The deconvolution procedure has been incorporated into a computer code. The application of that code to the deconvolution of CARS spectra obtained for samples at thermal equilibrium and not at thermal equilibrium is reported. The method is accurate and computationally efficient

SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2

Science.gov (United States)

Frost, Ray L.; López, Andrés; Scholz, Ricardo; Sampaio, Ney Pinheiro; de Oliveira, Fernando A. N.

2015-02-01

In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm-1 are assigned to the CO32- ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm-1 in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm-1 are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

Vibrational studies of Thyroxine hormone: Comparative study with quantum chemical calculations

Science.gov (United States)

Borah, Mukunda Madhab; Devi, Th. Gomti

2017-11-01

The FTIR and Raman techniques have been used to record spectra of Thyroxine. The stable geometrical parameters and vibrational wave numbers were calculated based on potential energy distribution (PED) using vibrational energy distribution analysis (VEDA) program. The vibrational energies are assigned to monomer, chain dimer and cyclic dimers of this molecule using the basis set B3LYP/LANL2DZ. The computational scaled frequencies are in good agreements with the experimental results. The study is extended to calculate the HOMO-LUMO energy gap, Molecular Electrostatic Potential (MEP) surface, hardness (η), chemical potential (μ), Global electrophilicity index (ω) and different thermo dynamical properties of Thyroxine in different states. The calculated HOMO-LUMO energies show the charge transfer occurs within the molecule. The calculated Natural bond orbital (NBO) analysis confirms the presence of intra-molecular charge transfer as well as the hydrogen bonding interaction.

The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

Energy Technology Data Exchange (ETDEWEB)

Vasilatou, K.; Michaud, J. M.; Baykusheva, D.; Grassi, G.; Merkt, F. [Laboratorium für Physikalische Chemie, ETH Zürich, CH-8093 Zurich (Switzerland)

2014-08-14

The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra of deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.

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

NARCIS (Netherlands)

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

2016-01-01

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

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

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

Calculation of the ex-core neutron noise induced by fuel vibrations in PWRs

International Nuclear Information System (INIS)

Tran Hoai Nam; Cao Van Chung; Hoang Thanh Phi Hung; Hoang Van Khanh

2015-01-01

Calculation of the neutron noise induced by fuel assembly vibrations in two pressurized water reactor (PWR) cores has been performed to investigate the effect of cycle burnup on the properties of the ex-core detector noise. Pendular vibrations of individual fuel assemblies were assumed to occur at different locations in the core. The auto power spectra density (APSD) of the ex-core detector noise was evaluated with the assumption of stochastic vibrations along a random two-dimensional trajectory. The results show that no general monotonic variation of APSD was found. The increase of APSD occurs predominantly for peripheral assemblies. Assuming simultaneous vibrations of a number of fuel assemblies uniformly distributed over the core with the more realistic perturbation model, the effect of the peripheral assemblies will dominate and the increase of the amplitude of the ex-core neutron noise with burnup can be confirmed. (author)

Experimental studies of flow induced vibrations of the fuel assembly for the PEC reactor

International Nuclear Information System (INIS)

Pitimada, D.; Presaghi, M.; Tampone, O.; Cesari, F.

1977-01-01

The vibration behaviour of an assembly of seven mock-up fuel bundles of PEC reactor has been investigated. The assembly was excited by a parallel flow of water simulating sodium. The motion of the group (or of a single bundle in the group) has been measured in transverse sections detecting two orthogonal components of displacement. During the experiences the following parameters were varied: bundle foot and pads restraints, flow rate condition, coolant flow outlet conditions at the head of fuel bundles. Experimental data were processed in order to obtain: trajectories of three points of fuel bundle axis, power density spectra of measured vibration amplitudes, correlations between coolant flow rate and vibration amplitude R.M.S. (author)

Molecular rotation-vibration dynamics of low-symmetric hydrate crystal in the terahertz region.

Science.gov (United States)

Fu, Xiaojian; Wu, Hongya; Xi, Xiaoqing; Zhou, Ji

2014-01-16

The rotational and vibrational dynamics of molecules in copper sulfate pentahydrate crystal are investigated with terahertz dielectric spectra. It is shown that the relaxation-like dielectric dispersion in the low frequency region is related to the reorientation of water molecules under the driving of terahertz electric field, whereas the resonant dispersion can be ascribed to lattice vibration. It is also found that, due to the hydrogen-bond effect, the vibrational mode at about 1.83 THz along [-111] direction softens with decreasing temperature, that is, the crystal expands in this direction when cooled. On the contrary, the mode hardens in the direction perpendicular to [-111] during the cooling process. This contributes to the further understanding of the molecular structure and bonding features of hydrate crystals.

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

Chains of benzenes with lithium-atom adsorption: Vibrations and spontaneous symmetry breaking

Science.gov (United States)

Ortiz, Yenni P.; Stegmann, Thomas; Klein, Douglas J.; Seligman, Thomas H.

2017-09-01

We study effects of different configurations of adsorbates on the vibrational modes as well as symmetries of polyacenes and poly-p-phenylenes focusing on lithium atom adsorption. We found that the spectra of the vibrational modes distinguish the different configurations. For more regular adsorption schemes the lowest states are bending and torsion modes of the skeleton, which are essentially followed by the adsorbate. On poly-p-phenylenes we found that lithium adsorption reduces and often eliminates the torsion between rings thus increasing symmetry. There is spontaneous symmetry breaking in poly-p-phenylenes due to double adsorption of lithium atoms on alternating rings.

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....

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.

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

Science.gov (United States)

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

2010-05-03

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

A computationally efficient software application for calculating vibration from underground railways

International Nuclear Information System (INIS)

Hussein, M F M; Hunt, H E M

2009-01-01

The PiP model is a software application with a user-friendly interface for calculating vibration from underground railways. This paper reports about the software with a focus on its latest version and the plans for future developments. The software calculates the Power Spectral Density of vibration due to a moving train on floating-slab track with track irregularity described by typical values of spectra for tracks with good, average and bad conditions. The latest version accounts for a tunnel embedded in a half space by employing a toolbox developed at K.U. Leuven which calculates Green's functions for a multi-layered half-space.

The electron–phonon coupling of fundamental, overtone, and combination modes and its effects on the resonance Raman spectra

Energy Technology Data Exchange (ETDEWEB)

Li, Shuo [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); College of Physics, Jilin University, Changchun 130012 (China); Li, Zhanlong; Wang, Shenghan; Gao, Shuqin [College of Physics, Jilin University, Changchun 130012 (China); Sun, Chenglin, E-mail: chenglin@jlu.edu.cn [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); College of Physics, Jilin University, Changchun 130012 (China); Li, Zuowei [College of Physics, Jilin University, Changchun 130012 (China)

2015-12-15

Highlights: • The Huang–Rhys factors and electron–phonon coupling constants are calculated. • The changes of overtone mode are larger than those of fundamental mode. • The variation pattern of electron–phonon coupling well interprets the changes of spectra. - Abstract: External field plays a very important role in the interaction between the π-electron transition and atomic vibration of polyenes. It has significant effects on both the Huang–Rhys factor and the electron–phonon coupling. In this paper, the visible absorption and resonance Raman spectra of all-trans-β-carotene are measured in the 345–295 K temperature range and it is found that the changes of the 0–1 and 0–2 vibration bands of the absorption spectra with the temperature lead to the different electron–phonon coupling of fundamental, overtone, and combination modes. The electron-phonon coupling constants of all the modes are calculated and analyzed under different temperatures. The variation law of the electron–phonon coupling with the temperature well interprets the changes of the resonance Raman spectra, such as the shift, intensity and line width of the overtone and combination modes, which are all greater than those of the fundamental modes.

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

Science.gov (United States)

Edler, J.; Hamm, P.

2003-08-01

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

The vibrational spectrum of the hydrated alanine-leucine peptide in the amide region from IR experiments and first principles calculations

Science.gov (United States)

Hassan, Irtaza; Donati, Luca; Stensitzki, Till; Keller, Bettina G.; Heyne, Karsten; Imhof, Petra

2018-04-01

We have combined infrared (IR) experiments with molecular dynamics (MD) simulations in solution at finite temperature to analyse the vibrational signature of the small floppy peptide Alanine-Leucine. IR spectra computed from first-principles MD simulations exhibit no distinct differences between conformational clusters of α -helix or β -sheet-like folds with different orientations of the bulky leucine side chain. All computed spectra show two prominent bands, in good agreement with the experiment, that are assigned to the stretch vibrations of the carbonyl and carboxyl group, respectively. Variations in band widths and exact maxima are likely due to small fluctuations in the backbone torsion angles.

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

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

Science.gov (United States)

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

2010-08-01

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

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.

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.

Intermediate energy electron impact excitation of composite vibrational modes in phenol

Energy Technology Data Exchange (ETDEWEB)

Neves, R. F. C. [School of Chemical and Physical Sciences, Flinders University, G.P.O. Box 2100, Adelaide, SA 5001 (Australia); Instituto Federal do Sul de Minas Gerais, Campus Poços de Caldas, Minas Gerais (Brazil); Departamento de Física, Universidade Federal de Juiz de Fora, 36036-900, Juiz de Fora, Minas Gerais (Brazil); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, G.P.O. Box 2100, Adelaide, SA 5001 (Australia); Lopes, M. C. A.; Nixon, K. L. [Departamento de Física, Universidade Federal de Juiz de Fora, 36036-900, Juiz de Fora, Minas Gerais (Brazil); Oliveira, E. M. de; Lima, M. A. P. [Instituto de Física ‘Gleb Wataghin,’ Universidade Estadual de Campinas, 13083-859 Campinas, São Paulo (Brazil); Costa, R. F. da [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, 09210-580 Santo André, São Paulo (Brazil); Varella, M. T. do N. [Instituto de Física, Universidade de São Paulo, C.P. 66318, 05315-970 São Paulo (Brazil); Bettega, M. H. F. [Departamento de Física, Universidade Federal do Paraná, C.P. 19044, 81531-990 Curitiba, Paraná (Brazil); Silva, G. B. da [Universidade Federal de Mato Grosso, Barra do Garças, Mato Grosso (Brazil); Brunger, M. J., E-mail: Michael.Brunger@flinders.edu.au [School of Chemical and Physical Sciences, Flinders University, G.P.O. Box 2100, Adelaide, SA 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia)

2015-05-21

We report differential cross section results from an experimental investigation into the electron impact excitation of a number of the low-lying composite (unresolved) vibrational modes in phenol (C{sub 6}H{sub 5}OH). The measurements were carried out at incident electron energies in the range 15–40 eV and for scattered-electron angles in the range 10–90°. The energy resolution of those measurements was typically ∼80 meV. Calculations, using the GAMESS code, were also undertaken with a B3LYP/aug-cc-pVDZ level model chemistry, in order to enable us to assign vibrational modes to the features observed in our energy loss spectra. To the best of our knowledge, the present cross sections are the first to be reported for vibrational excitation of the C{sub 6}H{sub 5}OH molecule by electron impact.

Franck-Condon Simulations including Anharmonicity of the Ã(1)A''-X̃(1)A' Absorption and Single Vibronic Level Emission Spectra of HSiCl and DSiCl.

Science.gov (United States)

Mok, Daniel W K; Lee, Edmond P F; Chau, Foo-Tim; Dyke, John M

2009-03-10

RCCSD(T) and/or CASSCF/MRCI calculations have been carried out on the X̃(1)A' and Ã(1)A'' states of HSiCl employing basis sets of up to the aug-cc-pV5Z quality. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HSiCl. Franck-Condon factors which include allowance for anharmonicity and Duschinsky rotation between these two states of HSiCl and DSiCl were calculated employing RCCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate the Ã(1)A'' ← X̃(1)A' absorption and Ã(1)A'' → X̃(1)A' single vibronic level (SVL) emission spectra of HSiCl and DSiCl. Simulated absorption and experimental LIF spectra, and simulated and observed Ã(1)A''(0,0,0) → X̃(1)A' SVL emission spectra, of HSiCl and DSiCl are in very good agreement. However, agreement between simulated and observed Ã(1)A''(0,1,0) → X̃(1)A' and Ã(1)A''(0,2,1) → X̃(1)A' SVL emission spectra of DSiCl is not as good. Preliminary calculations on low-lying excited states of HSiCl suggest that vibronic interaction between low-lying vibrational levels of the Ã(1)A'' state and highly excited vibrational levels of the ã(3)A'' is possible. Such vibronic interaction may change the character of the low-lying vibrational levels of the Ã(1)A'' state, which would lead to perturbation in the SVL emission spectra from these vibrational levels.

On-line vibration and loose parts monitoring of nuclear power stations as a preventive maintenance tool

International Nuclear Information System (INIS)

An equipment for on-line monitoring of vibrations and loose parts of nuclear power plants is described. The unit consists of piezoelectric transducers, preamplifiers, a data processor, and peripherals. It secures on-line measurement without interfering with the operation of the power plant. A diagram is given showing the monitor of vibrations and loose parts for pressurized water reactors and the Spectra-Scan equipment for the automatic recording and computer processing of noise signals is described. A survey is given of diagnostic methods for internal vibrations, noise and oscillations and procedures for the analysis of recordings are described. The experiences of Atomica International with the observation of vibrations in nuclear power plants are described and an economic assessment is presented of the efficiency of on-line monitoring of these vibrations. A cost-benefit analysis is made of such equipment which justifies their introduction. (B.S.)

An analysis of vibration-rotation lines of OH in the solar infrared spectrum

NARCIS (Netherlands)

Grevesse, N.; Sauval, A.J.; Dishoeck, van E.F.

1984-01-01

High resolution solar spectra have permitted the measurement with great accuracy of equivalent widths of vibration-rotation lines of OH in the X2Pi state near 3-micron wavelength. Using recent theoretical results for the transition probabilities, a solar oxygen abundance of (8.93 + or - 0.02) is

Analysis of flow induced vibration in heat exchangers

International Nuclear Information System (INIS)

Beek, A.W. van

1977-01-01

A description will be given of three different types of heat exchangers developed by the Dutch Nuclear Industry Group ''Neratoom'' in cooperation with TNO for the sodium-cooled fast breeder reactor SNR-300 at Kalkar. Moreover, the research related with flow induced vibrations carried out by TNO (Organization for Applied Scientific Research) will be presented. The flow induced forces on the tubes of the straight-tube steam generators were measured at the inlet and outlet section where partial crossflow occurs. With the measured flow induced forces the response of a tube was calculated as a function of the tube-to-supportbush clearances taking into account the non-linear damping effects from the sodium. The theoretical results showed that for this particular design no tube impact damage is to be expected which was confirmed later by a full scale experiment. Special attention will be devoted to the steam generator with helical-coil tube-bundles, where the sodium flows in a counter cross-flow over the tube-bundle. Extensive measurements of the power spectra of the flow induced forces were carried out since no information could be found in the literature. The vibration analysis will be presented and vibration modes of the entire bundle will be compared with experimentally obtained results. Finally a description of the vibration tests to be carried out on the intermediate heat exchanger (IHX) will be presented. (author)

Analysis of flow induced vibration in heat exchangers

Energy Technology Data Exchange (ETDEWEB)

Beek, A.W. van [Institute for Mechanical Constructions TNO, Delft (Netherlands)

1977-12-01

A description will be given of three different types of heat exchangers developed by the Dutch Nuclear Industry Group ''Neratoom'' in cooperation with TNO for the sodium-cooled fast breeder reactor SNR-300 at Kalkar. Moreover, the research related with flow induced vibrations carried out by TNO (Organization for Applied Scientific Research) will be presented. The flow induced forces on the tubes of the straight-tube steam generators were measured at the inlet and outlet section where partial crossflow occurs. With the measured flow induced forces the response of a tube was calculated as a function of the tube-to-supportbush clearances taking into account the non-linear damping effects from the sodium. The theoretical results showed that for this particular design no tube impact damage is to be expected which was confirmed later by a full scale experiment. Special attention will be devoted to the steam generator with helical-coil tube-bundles, where the sodium flows in a counter cross-flow over the tube-bundle. Extensive measurements of the power spectra of the flow induced forces were carried out since no information could be found in the literature. The vibration analysis will be presented and vibration modes of the entire bundle will be compared with experimentally obtained results. Finally a description of the vibration tests to be carried out on the intermediate heat exchanger (IHX) will be presented. (author)

Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

Energy Technology Data Exchange (ETDEWEB)

Ringholm, Magnus; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø – The Arctic University of Norway, 9037 Tromsø (Norway); Bast, Radovan [Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, AlbaNova University Center, S-10691 Stockholm (Sweden); PDC Center for High Performance Computing, Royal Institute of Technology, S-10044 Stockholm (Sweden); Oggioni, Luca [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø – The Arctic University of Norway, 9037 Tromsø (Norway); Department of Physics G. Occhialini, University of Milano Bicocca, Piazza della scienza 3, 20126 Milan (Italy); Ekström, Ulf [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo (Norway)

2014-10-07

We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

Vibrational spectroscopic investigation of p-, m- and o-nitrobenzonitrile by using Hartree-Fock and density functional theory

Science.gov (United States)

Sert, Y.; Ucun, F.

2013-08-01

In the present work, the theoretical vibrational spectra of p-, m- and o-nitrobenzonitrile molecules have been analyzed. The harmonic vibrational frequencies and geometric parameters (bond lengths and bond angles) of these molecules have been calculated using ab initio Hartree-Fock and density functional theory methods with 6-311++G(d,p) basis set by Gaussian 03 W, for the first time. Assignments of the vibrational frequencies have been performed by potential energy distribution by using VEDA 4 program. The optimized geometric parameters and harmonic vibrational frequencies have been compared with the corresponding experimental data and seen to be in a good agreement with each other. Also, the highest occupied molecular orbital and lowest unoccupied molecular orbital energies have been obtained.

Multifocus confocal Raman microspectroscopy for fast multimode vibrational imaging of living cells.

Science.gov (United States)

Okuno, Masanari; Hamaguchi, Hiro-o

2010-12-15

We have developed a multifocus confocal Raman microspectroscopic system for the fast multimode vibrational imaging of living cells. It consists of an inverted microscope equipped with a microlens array, a pinhole array, a fiber bundle, and a multichannel Raman spectrometer. Forty-eight Raman spectra from 48 foci under the microscope are simultaneously obtained by using multifocus excitation and image-compression techniques. The multifocus confocal configuration suppresses the background generated from the cover glass and the cell culturing medium so that high-contrast images are obtainable with a short accumulation time. The system enables us to obtain multimode (10 different vibrational modes) vibrational images of living cells in tens of seconds with only 1 mW laser power at one focal point. This image acquisition time is more than 10 times faster than that in conventional single-focus Raman microspectroscopy.

Vibrational Investigations of Silver-Doped Hydroxyapatite with Antibacterial Properties

Directory of Open Access Journals (Sweden)

Carmen Steluta Ciobanu

2013-01-01

Full Text Available 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 most intense peak Raman spectrum is the narrow band observed at 960 cm−1. In this article Ag:HAp-NPs were also evaluated for their antimicrobial activities against gram-positive, gram-negative, and fungal strains. The specific antimicrobial activity revealed by the qualitative assay demonstrates that our compounds are interacting differently with the microbial targets.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-01

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

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.

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

Torsional vibration signal analysis as a diagnostic tool for planetary gear fault detection

Science.gov (United States)

Xue, Song; Howard, Ian

2018-02-01

This paper aims to investigate the effectiveness of using the torsional vibration signal as a diagnostic tool for planetary gearbox faults detection. The traditional approach for condition monitoring of the planetary gear uses a stationary transducer mounted on the ring gear casing to measure all the vibration data when the planet gears pass by with the rotation of the carrier arm. However, the time variant vibration transfer paths between the stationary transducer and the rotating planet gear modulate the resultant vibration spectra and make it complex. Torsional vibration signals are theoretically free from this modulation effect and therefore, it is expected to be much easier and more effective to diagnose planetary gear faults using the fault diagnostic information extracted from the torsional vibration. In this paper, a 20 degree of freedom planetary gear lumped-parameter model was developed to obtain the gear dynamic response. In the model, the gear mesh stiffness variations are the main internal vibration generation mechanism and the finite element models were developed for calculation of the sun-planet and ring-planet gear mesh stiffnesses. Gear faults on different components were created in the finite element models to calculate the resultant gear mesh stiffnesses, which were incorporated into the planetary gear model later on to obtain the faulted vibration signal. Some advanced signal processing techniques were utilized to analyses the fault diagnostic results from the torsional vibration. It was found that the planetary gear torsional vibration not only successfully detected the gear fault, but also had the potential to indicate the location of the gear fault. As a result, the planetary gear torsional vibration can be considered an effective alternative approach for planetary gear condition monitoring.

Linearised collective Schroedinger equation for nuclear quadrupole surface vibrations

International Nuclear Information System (INIS)

Greiner, M.; Heumann, D.; Scheid, W.

1990-11-01

The linearisation of the Schroedinger equation for nuclear quadrupole surface vibrations yields a new spin degree of freedom, which is called collective spin and has a value of 3/2. With the introduction of collective spin dependent potentials, this linearised Schroedinger equation is then used for the description of low energy spectra and electromagnetic transition probabilities of some even-odd Xe, Ir and Au nuclei which have a spin 3/2 in their groundstate. (orig.)

Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

Science.gov (United States)

Latouche, Camille; Bloino, Julien; Barone, Vincenzo

2014-06-01

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

Examination and vibration characteristics of gas circulator (B1) of HENDEL

International Nuclear Information System (INIS)

Shimomura, Hiroaki; Izawa, Naoki; Ihzuka, Takayuki; Kawaji, Satoshi; Kunitama, Takehiko; Hayashi, Haruyoshi; Kobayashi, Toshiaki; Katoh, Michio

1985-06-01

An examination and vibration measurements were conducted on the gas bearing type high speed helium gas circulator after the failure on April 1984 and the repairing on August 1984. The examination made clear that the cause of the failure and scratching of gas bearing pads and journal shaft was found. The vibrational spectra showed a clear difference between failed and repaired conditions, and a frequency analysis technique by means of fast Fourier transform and a small-scale computer is expected as a useful method of diagnosis for circulators. A conceptual scheme of gas circulator diagnostic system based on above principle is shown, and a basic process of diagnostic software is described. (author)

Vibrational signatures of cation-anion hydrogen bonding in ionic liquids: a periodic density functional theory and molecular dynamics study.

Science.gov (United States)

Mondal, Anirban; Balasubramanian, Sundaram

2015-02-05

Hydrogen bonding in alkylammonium based protic ionic liquids was studied using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Normal-mode analysis within the harmonic approximation and power spectra of velocity autocorrelation functions were used as tools to obtain the vibrational spectra in both the gas phase and the crystalline phases of these protic ionic liquids. The hydrogen bond vibrational modes were identified in the 150-240 cm(-1) region of the far-infrared (far-IR) spectra. A blue shift in the far-IR mode was observed with an increasing number of hydrogen-bonding sites on the cation; the exact peak position is modulated by the cation-anion hydrogen bond strength. Sub-100 cm(-1) bands in the far-IR spectrum are assigned to the rattling motion of the anions. Calculated NMR chemical shifts of the acidic protons in the crystalline phase of these salts also exhibit the signature of cation-anion hydrogen bonding.

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

Science.gov (United States)

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

2017-11-06

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

Study by vibration spectrometry of addition compounds of boron fluoride with some alkyl oxides, sulphides and selenides

International Nuclear Information System (INIS)

Le Calve, Jacques

1966-01-01

This research thesis reports the study of the vibration spectrum of some addition compounds of boron fluoride with alkyl oxides, sulphides and selenides. The objective was first the assignment of spectra, and then the study of the influence of the formation of a coordination bound on boron fluoride vibrations and on that of its donor. The author also tried to define correlations between spectrum and structures, and studied the effects of physical status and solvents [fr

Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory

Science.gov (United States)

Borah, Mukunda Madhab; Devi, Th. Gomti

2018-06-01

The vibrational spectral analysis of Serotonin and its dimer were carried out using the Fourier Transform Infrared (FTIR) and Raman techniques. The equilibrium geometrical parameters, harmonic vibrational wavenumbers, Frontier orbitals, Mulliken atomic charges, Natural Bond orbitals, first order hyperpolarizability and some optimized energy parameters were computed by density functional theory with 6-31G(d,p) basis set. The detailed analysis of the vibrational spectra have been carried out by computing Potential Energy Distribution (PED, %) with the help of Vibrational Energy Distribution Analysis (VEDA) program. The second order delocalization energies E(2) confirms the occurrence of intramolecular Charge Transfer (ICT) within the molecule. The computed wavenumbers of Serotonin monomer and dimer were found in good agreement with the experimental Raman and IR values.