Theoretical Study on the Excited Electronic States of CHCl: Application to Photodissociation at 193 nm.

Abstract

We present herein a high-level ab initio study on the electronic excited states of CHCl using the internally contracted multireference configuration interaction method including Davidson correction (icMRCI+Q). A total of 13 electronic states with energy of up to 7 eV have been investigated. The vertical transition energies, oscillator strengths, electron configurations, and transitions of the electronic states of CHCl have been calculated at the icMRCI+Q/aug-cc-pv(5+d)Z level. The potential energy curves of the electronic states have been studied along the H-C-Cl angle, the C-H bond length, and the C-Cl bond length, respectively. Our theoretical study has provided comprehensive information for understanding the interaction and the behavior of the electronic excited states of CHCl. In particular, the excited state involved in the 193 nm photodissociation as well as the corresponding dissociation dynamics have been discussed on the basis of our calculation results. The present study should shed more light on the photochemistry of CHCl in the ultraviolet region.