Photodissociation of bromobenzene, dibromobenzene, and 1,3,5-tribromobenzene
2004 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 120, no 14, 6502-6509 p.Article in journal (Refereed) Published
Quantum chemical calculations have been performed on the ground state and several low-lying excited states of bromobenzene, ortho-, meta-, and para-dibromobenzene, and 1,3,5-tribromobenzene using high-level ab initio and hybrid density-functional methods. Experimental observations of ultrafast predissociation in these molecules are clarified from extensive theoretical information about all low-energy potential-energy curves together with symmetry arguments. The intriguing observation that o- and m-dibromobenzene have two ultrafast predissociation channels while bromobenzene, p-dibromobenzene, and 1,3,5-tribromobenzene only have one such channel is explained from the calculated potential-energy curves. These show that the lowering of point-group symmetry from C-2v to C-s along the main photodissociation reaction coordinate, which only occurs in o- and m-dibromobenzene, opens up a new predissociation channel. Dynamical quantum simulations based on the calculated potential-energy curves are used to estimate the coupling strength at the intersystem crossing point in bromobenzene. (C) 2004 American Institute of Physics.
Place, publisher, year, edition, pages
2004. Vol. 120, no 14, 6502-6509 p.
IdentifiersURN: urn:nbn:se:uu:diva-144159DOI: 10.1063/1.1667460ISI: 000220456400019OAI: oai:DiVA.org:uu-144159DiVA: diva2:392740