Search results for "Vibrational spectroscopy"
showing 10 items of 85 documents
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…
Symmetry of molecular properties
1993
The symmetry of coefficients in the expansion of a given molecular property are shown to be obtainable through well defined tensor methods. The analytical expansions required of various vibrational and rotational tensors are given up to the fourth degree in dynamical variables. To illustrate the method, some rovibrational properties of spherical tops are considered. The symmetry of the associated molecular constants is expressed, simultaneously, for XY4 and XY6 molecules, by algebraic relations involving the independent constants and the coupling symbols of the molecular symmetry group. To allow comparisons, some examples are given for which the symmetry of the constants has been published …
Development of the Hamiltonian and transition moment operators of symmetric top molecules using the O(3)⊃C∞v⊃C3v group chain
2005
Abstract We present a development of the Hamiltonian, dipole moment, and polarizability operators for XY3Z molecules. These rovibrational operators are written with the aid of a tensorial formalism derived from the one already used in Dijon and adapted to the XY3Z symmetric tops in a recent paper [A. El Hilali, V. Boudon, M. Loete, J. Mol. Spectrosc. 234 (2005) 166–174]. We use the O (3) ⊃ C∞v ⊃ C3v group chain. Expressions for the matrix elements are derived for these operators.
Spectroscopy of XY5Z (C4v) Molecules: Development of the Hamiltonian and the Transition Moment Operators Using a Tensorial Formalism
2000
We present a development of the Hamiltonian, dipole moment, and polarizability operators of XY(5)Z (C(4v)) molecules using a tensorial formalism derived from the one developed previously in Dijon for XY(6) molecules. These operators are involved in the calculation of the energies and intensities of rovibrational transitions and are essential for spectrum simulations. Expressions for the matrix elements are derived for all these operators. Copyright 2000 Academic Press.
A local picture associated with a triply degenerate vibrational mode: vibrational and rovibrational local states
1998
International audience; Abstract: A symmetrized basis adapted to the study of some vibrational excited states of spherical top molecules is proposed. This basis, consistent with the Cartesian picture associated with a three-dimensional mode, is then tested numerically through various XY6 and XY4 molecules. In addition, some simulations, made with 238UF6 and a simplified version of an effective Hamiltonian, clearly show that the method can be further extended through the construction of a symmetrized local rovibrational basis.
Organization of Quantum Bifurcations: Crossover of Rovibrational Bands in Spherical Top Molecules
1989
Qualitative changes in the rotational structure of a finite particle quantum system are studied. The crossover phenomenon is explained from the point of view of consecutive quantum bifurcations. The generic organization of bifurcations is related to the stratification of the space of dynamical variables imposed by the invariance group of the Hamiltonian.
Rovibrational structure of the Ar–CO complex based on a novel three-dimensional ab initio potential
2002
The first three-dimensional ab initio intermolecular potential energy surface of the Ar–CO van der Waals complex is calculated using the coupled cluster singles and doubles including connected triples model and the augmented correlation-consistent polarized valence quadruple zeta (aug-cc-pVQZ) basis set extended with a (3s3p2d1f1g) set of midbond functions. The three-dimensional surface is averaged over the three lowest vibrational states of CO. Rovibrational energies are calculated up to 50 cm−1 above the ground state, thus enabling comprehensive comparison between theory and available experimental data as well as providing detailed guidance for future spectroscopic investigations of highe…
Intermolecular potential and rovibrational states of the H2O–D2 complex
2012
International audience; A five-dimensional intermolecular potential for H2O-D-2 was obtained from the full nine-dimensional ab initio potential surface of Valiron et al. [P. Valiron, M. Wernli, A. Faure, L. Wiesenfeld, C. Rist, S. Kedzuch, J. Noga, J. Chem. Phys. 129 (2008) 134306] by averaging over the ground state vibrational wave functions of H2O and D-2. On this five-dimensional potential with a well depth D-e of 232.12 cm (1) we calculated the bound rovibrational levels of H2O-D-2 for total angular momentum J = 0-3. The method used to compute the rovibrational levels is similar to a scattering approach-it involves a basis of coupled free rotor wave functions for the hindered internal r…
Spherical top data system (STDS) software for the simulation of spherical top spectra
1998
Abstract The Spherical Top Data System (STDS) software package for the simulation of spherical top spectra is presented. It consists of a single UNIX script with self-explanatory arguments allowing the non-expert user to calculate spectra from the results of the high resolution analyses performed over the recent decades on this type of molecules. More than one hundred parameter files are presently available including various band systems of 16 molecular species (among which methane is the most documented) and various types of calculations: rovibrational energy levels, i.r. absorption, Raman scattering and Stark coefficients. STDS is freely accessible by anonymous ftp at jupiter.u-bourgogne.…