An ab initio investigation of the mechanisms of photodissociationin bromobenzene and iodobenzene

摘要

In concert with the latest experiment of velocity imaging technique [X. P. Zhang et al.,ChemPhysChem 9, 1130 (2008)], quantum chemical calculations with relativistic effect wereperformed on the photodissociation of bromobenzene (BrPh) and iodobenzene (IPh) at 266 nm. Themethod of multistate second order multiconfigurational perturbation theory in conjunction withspin-orbit interaction through complete active space state interaction was employed to calculate thepotential energy curves for the ground and low-lying excited states of BrPh and IPh along theirphotodissociation reaction coordinates. The dissociation mechanisms with products of X(~2P_(3/2)) andX~*(~2P_(1/2)) (X=Br,I) states were clarified.