Time-dependent Wave Packet Quantum Scattering Study of Reaction S(3P)+H2→HS+H on a Newab initioPotential Energy Surface 3A′

Abstract

A new potential energy surface is presented for the triplet state 3A′ of the chemical reaction S(3P)+H2 from a set of accurate ab initio data. The single point energies are computed using highly correlated complete active space self-consistent-field and multi-reference configuration interaction wave functions with a basis set of aug-cc-pV5Z. We have fitted the full set of energy values using many-body expansion method with an Aguado-Paniagua function. Based on the new potential energy surface, we carry out the time-dependent wave packet scattering calculations over the collision energy range of 0.8-2.2 eV. Both the centrifugal-sudden approximation and Coriolis Coupling cross sections are obtained. In addition, the total reaction probabilities are calculated for the reactant H2 initially in the vibrational states v=0–3 (j=0). It is found that initial vibrational excitation enhances the title reaction.