Toward a fully automated calculation of rovibrational infrared intensities for semi-rigid polyatomic molecules.

Abstract

The implementation of a new program for the variational calculation of rovibrational state energies and infrared intensities is presented. The program relies on vibrational self-consistent field and vibrational configuration interaction theory and is based on the Watson Hamiltonian. All needed prerequisites, i.e., multidimensional potential energy and dipole moment surfaces, comprehensive symmetry information, the determination of vibrational wave functions, and an efficient calculation of partition functions, are computed in a fully automated manner, which allows us to calculate rovibrational spectra in a black-box type fashion. Moreover, the use of a molecule specific rotational basis leads to reliable rovibrational line lists. Benchmark calculations are provided for thioformaldehyde (H2CS), which shows strong Coriolis coupling effects and a complex rovibrational spectrum. The underlying multidimensional potential energy surface has been calculated at the level of explicitly correlated coupled-cluster theory.