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 |
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Hauptverfasser: | , , , |
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%. |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/1.470485 |