Spectroscopy and dynamics of the isolated sp2 CH chromophore in trideuteroacetaldehyde CD3CHO as derived from extrapolated SDCI ab initio calculations

Abstract

Ab initio CI potential energy (PES) and dipole moment (DMS) surfaces have been calculated with singles and doubles excitation configuration interaction (SDCI) for the 2-dimensional isolated sp2 CH chromophore subspace of trideuteroacetaldehyde (CD3CHO). Different extrapolation schemes to full-CI have been applied after the extrapolation to full-SDCI. Vibrational band centres and absolute intensities are determined variationally on six extrapolated surfaces. The band centres are analysed within the effective Hamiltonian model for isolated CH chromophores and the effective spectroscopic parameters are compared for the different extrapolation schemes. Time dependent population evolution for vibrational quantum motion with a pure CH stretching state being initially populated is calculated for some of the extrapolated surfaces within the effective Hamiltonian model.