Reduced Dimensionality Approaches in Quantum Dynamics. Ozone Photodissociation including Nonadiabatic Effects

摘要

The singlet-to-triplet ratio in the ozone UV-photodissociation process was estimated using the 1D effective Hamiltonian. Effective Hamiltonian was very similar to the Reaction Path Hamiltonian proposed by Miller, Handy and Adams. Energies for eight singlet electronic states of ozone along a reaction path were calculated by multistate quasidegenerate perturbation theory (MCQDPT) with state-averaged multiconfigurational self-consistent field's wavefunctions. Diabatic states were built by smooth interpolation of the ab initio points in the vicinity of quasi-crossings. Subsequent quantum dynamics simulations were made in the wave-packet approach using computer program written by authors. The influence of nonadiabatic interactions onto absorption spectrum was estimated.