Search results for "vibration"
showing 10 items of 823 documents
Quantum dynamics of the photostability of pyrazine
2015
We investigate the radiationless decay of photoexcited pyrazine to its ground electronic state using multireference electronic structure and quantum dynamics calculations. We construct a quadratic vibronic coupling Hamiltonian, including the four lowest electronic states and ten vibrational modes, by fitting to more than 5000 ab initio points. We then use this model to simulate the non-adiabatic excited state dynamics of the molecule using the multi-configuration time-dependent Hartree method. On the basis of these calculations, we propose a new mechanism for this decay process involving a conical intersection between the Au(nπ*) state and the ground state. After excitation to the B2u(ππ*) …
High-resolution spectroscopy and analysis of the stretching dyad of osmium tetroxide
2011
Abstract OsO4 is a heavy tetrahedral molecule that may constitute a benchmark for quantum chemistry calculations. Its favorable spin statistics (due to the zero nuclear spin of oxygen atoms) is such that only A1 and A2 rovibrational levels are allowed, leading to a dense, but quite easily resolved spectrum. Most lines are single ones, instead of complex line clusters as in the case of other heavy spherical-tops like SF6, for instance. It is thus possible to fully assign and fit the spectrum and to obtain precise experimental effective molecular parameters. The strong ν 3 stretching fundamental has been studied a long time ago as an isolated band [McDowell RS, Radziemski LJ, Flicker H, Galbr…
top data system ( TDS) software for infrared spectrum simulation of asymmetric molecules: some improvements to the TDS packages
2005
Abstract The spherical top data system (STDS) program suite developed in Dijon has been extended with the aim of studying any rovibrational band or polyad of XY 2 Z 2 ( C 2 v ) asymmetric top molecules. We work in the O ( 3 ) ⊃ T d ⊃ C 2 v chain because these species result from the substitution of two ligands of a corresponding “parent” spherical top and thus are relatively close to tetrahedral symmetry. The choice of this group chain has consequences on the method used to specify the input parameters of the programs for Hamiltonian and transition moment model calculations. One example concerning the ground state of the SO2F2 quasi-spherical molecule is presented. As before, this suite con…
C4v Top Data System (C4v TDS) software for infrared spectrum simulation of XY5Z symmetric molecules
2002
Abstract The Highly spherical Top Data System program suite developed in Dijon has been extended in the aim of studying any rovibrational band or polyad of XY5Z (C4v) symmetric top molecules. We work in the O(3)⊃Oh⊃C4v chain because most of these species result from the substitution of one ligand of the corresponding spherical tops and thus are relatively close to octahedral symmetry. The choice of this group chain has consequences in the way in which it is used to specify the input parameters of the programs for Hamiltonian and transition moment model calculations. One example concerning the ν1/ν8 dyad of the SF 5 35 Cl molecule is presented. As before, this suite consists of a series of F…
New assignments in the 2μm transparency window of the 12CH4 Octad band system
2013
Abstract This paper reports new assignments of rovibrational transitions of 12 CH 4 bands in the range 4600–4887 cm −1 which is usually referred to as a part of the 2 μm methane transparency window. Several experimental data sources for methane line positions and intensities were combined for this analysis. Three long path Fourier transform spectra newly recorded in Reims with 1603 m absorption path length and pressures of 1, 7 and 34 hPa for samples of natural abundance CH 4 provided new measurements of 12 CH 4 lines. Older spectra for 13 CH 4 (90% purity) from JPL with 73 m absorption path length were used to identify the corresponding lines. Most of the lines in this region belong to th…
Line positions and intensities in the band of ethylene near : An experimental and theoretical study
2008
Abstract Recently, we built a tensorial formalism adapted to the spectroscopy of X2Y4 molecules. It is based on formalisms developed in Dijon for spherical-top molecules. This approach has the advantages to allow a systematic development of rovibrational interactions and to make global analyses easier to perform. We used this tool to carry out an analysis of the ν 12 band of 12C2H4 near 1450 cm - 1 , both in frequencies and intensities. 1240 line positions and 871 intensities, measured in a set of spectra recorded in Brussels, with global root mean square deviations of 1.6 × 10 - 4 cm - 1 and 1.88 % , respectively.
Pressure broadening, shift, and interference effect for a multiplet line in the rovibrational anisotropic stimulated raman spectrum of molecular oxyg…
1996
0022-2852; High-resolution stimulated inverse Raman spectroscopy has been applied to the study of collisional broadening, shifting, and line mixing for the O-o(J, N = 5) triplet line of the fundamental vibrational band of molecular oxygen. Accurate line broadening coefficients for the individual J components within the triplet have been measured for the first time and show a significant J dependence. The line broadening coefficients are larger than those previously obtained for unresolved pure rotational Raman lines. The additional broadening is expected to result from electronic spin relaxation. The pressure-induced line shift has been obtained for this Line and compared to the value obtai…
The Study Of The Nuclear Motion In D2+ Molecular Ion By Using The Harmonic Spectra
2007
In this paper we show how it is possible to investigate the nuclei dynamics of a D2+ molecular ion by using the high harmonic generation spectra emitted by the system when subjected to an intense laser field. In particular, the emitted spectra contains, in addition to the usual odd harmonic peaks, additional satellite peaks whose frequency spacing is equal to the vibrational frequency of the nuclei.
Evidence of Nuclear Motion in H2-like Molecule by Means of High Order Harmonic Generation
2008
The dynamics of hydrogen-like molecules is investigated beyond the usual fixed nuclei approximation. The nuclear motion introduces in the familiar spectrum of emitted radiation additional regular lines whose separation is essentially given by the vibrational frequency of nuclear motion. A wavelet analysis of the emitted spectrum shows that the intensity of the harmonic lines is modulated with the same period of the nuclear motion; this suggests the possibility of the real-time control of the nuclear dynamics.
Identification of Bending Modes of Vibration in Rails by a Laser Doppler Vibrometer on a Moving Platform
2020
This paper introduces a method to identify the bending modes of vibration of railway tracks by using a laser Doppler vibrometer (LDV) mounted on a moving platform. Two sets of experiments were conducted at Transportation Technology Center Inc. (TTCI) in Pueblo Colorado, in order to validate the proposed method. First, the bending vibration modes were identified using the signals collected from a rail span (rail section between two consecutive sleepers) by accelerometers under moving car excitation. Then, vibration measurements from rail spans were obtained by using an LDV mounted on the moving railcar. All tests were carried out at four different rail car speeds: 8 km/h (5 mph), 16 km/h (10…