Spin–Orbit Ab Initio Investigation of the Photolysis of Bromoiodomethane

TitleSpin–Orbit Ab Initio Investigation of the Photolysis of Bromoiodomethane
Publication TypeJournal Article
Year of Publication2006
AuthorsYa-Jun L, Devarajan A, Krogh JW, Tarnovsky AN, Lindh R
Journal TitleChemPhysChem
Keywordsab initio calculations, ABSORPTION, isomers, photochemistry, transition states

The photodissociation of bromoiodomethane has been investigated by spin–orbit ab initio calculations. The experimentally observed A- and B-bands and the corresponding photoproducts were assigned by multistate second-order multiconfigurational perturbation theory in conjunction with spin–orbit interaction through complete active space state interaction potential energy curves, vertical excitation energies, and oscillator strengths of low-lying excited states. The present conclusions with respect to the dissociation process in the B-band are different compared with those of previous studies. The reaction between the iso-CH2Br-I and iso-CH2I-Br species has also been studied. Finally, a set of stable excited states was identified for both isomers. These species might be of importance in the recombination process that follows the photodissociation in a solvent.