New accurate diabatic potential energy surfaces for the two lowest 1A′′ states of H2S and photodissociation dynamics in its first absorption band

Abstract

In this work, state-to-state photodissociation dynamics of H₂S in its first absorption band has been studied quantum mechanically with a new set of coupled potential energy surfaces (PESs) for the first two ¹A′′ excited states, which were developed at the explicitly correlated internally contracted multi-reference configuration interaction level with the cc-pVQZ-F12 basis set and a large active space. The calculated absorption spectrum, product state distributions, and angular distributions are in excellent agreement with available experimental data, validating the accuracy of the PESs and the non-adiabatic couplings. Detailed analysis of the dynamics reveals that there are strong non-adiabatic couplings between the bound 1¹B₁ and dissociative 1¹A₂ states around the Franck–Condon region, leading to very fast predissociation to ro-vibrationally cold SH() fragments, during which marginal angular anisotropy of the PESs is involved. This study provides quantitatively accurate characterization of the electronic structure and detailed fragmentation dynamics of this prototypical photodissociation system, which is desirable for improving astrochemical modelling.