화학공학소재연구정보센터
Journal of Chemical Physics, Vol.103, No.8, 2974-2982, 1995
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 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 Delta v = 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%.