Spin-orbit ab initio investigation of the photolysis of bromoiodomethane.
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-CH(2)Br-I and iso-CH(2)I-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.
Liu
Ya-Jun
YJ
Department of Theoretical Chemistry, Chemical Center, Lund University, P.O. Box 124, 221 00 Lund, Sweden.
Ajitha
Devarajan
D
Krogh
Jesper Wisborg
JW
Tarnovsky
Alexander N
AN
Lindh
Roland
R
D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry*; D010782:Photolysis; D011789:Quantum Theory; D014732:Vibration
D005609:Free Radicals; D006846:Hydrocarbons, Halogenated; C521928:bromoiodomethane; D008697:Methane