title: Relativistic multireference calculation of photodissociation of o-, m-, and p-bromofluorobenzene.
abstract: Quantum chemical calculations with relativistic effects were performed on the photodissociation of o-, m-, and p-bromofluorobenzene (o-, m-, and p-BrFPh) at 266 nm. The method of multistate second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction was employed to calculate the potential energy curves for the ground and low-lying excited states of o-, m-, and p-BrFPh along their photodissociation reaction coordinates. The dissociation mechanisms with products of Br((2)P(3∕2)) and Br(∗)((2)P(1∕2)) states were clarified with the computed potential energy curves and the surface crossings. The current calculations augmented previous theoretical investigations by including relativistic effects and resolved some differences of experimental assignment regarding the dissociation channels of o-, m-, and p-BrFPh.
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China.
authors.forename: Wen-Zuo
authors.initials: WZ
authors.lastname: Li
authors.forename: Shu-Feng
authors.initials: SF
authors.lastname: Chen
authors.forename: Ya-Jun
authors.initials: YJ
authors.lastname: Liu