title: Spin-orbit Ab initio investigation of the photodissociation of dibromomethane in the gas and solution phases.
abstract: A clear and reliable theoretical investigation on dibromomethane (CH(2)Br(2)) photodissociation is desired. The calculation must consider: (i) relativistic effects; (ii) the potential energy curves (PECs) of spin-orbit coupling states; (iii) geometry optimization by the method with both static and dynamic electron correlations; (iv) solvent effects on the photodissociation in the solution. All these have been considered in this study by state-of-the-art quantum chemical calculations. The experimentally observed photodissociation in the gas phase with products of spin-orbit-coupled states, Br((2)P(3/2)) and Br*((2)P(1/2)), was assigned by multi-state second order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction (MS-CASPT2/CASSI-SO) PECs. The mechanisms of the experimentally observed photodissociation and photoisomerization in solvent were elucidated by the MS-CASPT2/CASSI-SO method combined with polarized continuum model of the solvent.
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China.
authors.forename: Yajun
authors.initials: Y
authors.lastname: Liu
authors.forename: Hongyan
authors.initials: H
authors.lastname: Xiao
authors.forename: Mengtao
authors.initials: M
authors.lastname: Sun
authors.forename: Weihai
authors.initials: W
authors.lastname: Fang