Spectrum and dynamics of the CH chromophore in CD 2HF. II. Ab initio calculations of the potential and dipole moment functions

Abstract

We report ab initio (SCF-MP2 and CI) calculations on the three-dimensional anharmonic potential and dipole functions of the coupled vibrational modes of the CH chromopore in CD 2HF. Predictions of fundamental and overtone spectra are obtained from 3D solutions of the vibrational Schrödinger equation and are compared with experiment. The dominant Fermi and Darling-Dennison coupling constants in the effective Hamiltonian representation of experiment and theory agree well. Predicted overtone band strengths are satisfactory and very sensitive to the dipole function used.