Vibrational transitions of coupled stretching and bending overtones in chloroform

The intensities and frequencies of Fermi-coupled stretching and bending overtone transitions in CHCl3 were calculated by means of a variational method. Symmetrized two-dimensional ab initio potential and dipole moment surfaces were determined at the MP2 level using the 6-31G** basis set. The Hamilto...

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Veröffentlicht in:The Journal of chemical physics 1995-08, Vol.103 (8), p.2974-2982
Hauptverfasser: Beckmann, Kai, Gerhards, Markus, Kleist, Einhard, Bettermann, Hans
Format: Artikel
Sprache:eng
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Zusammenfassung:The intensities and frequencies of Fermi-coupled stretching and bending overtone transitions in CHCl3 were calculated by means of a variational method. Symmetrized two-dimensional ab initio potential and dipole moment surfaces were determined at the MP2 level using the 6-31G** basis set. The Hamiltonian for the CH- stretching motion and the simultaneously excited twofold degenerate CH- bending vibration is expressed most easily in cylindrical coordinates. Absorption intensities up to the Δv=7 CH-stretching overtone above 16 300 cm−1 are calculated and are compared to former experimental values and theoretical results. New quantitative intracavity measurements for the N=6 polyad are presented. Relative errors between absolute experimental intensities and the calculated values are less than 30%.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.470485