A theoretical study of bond selective photochemistry in CH2Brl -: art. no. 044310

Bromoiodomethane photodissociation in the low-lying excited states has been characterized using unrestricted Hartree-Fock, configuration-interaction- singles, and complete active space self-consistent field calculations with the SDB-aug-cc-pVTZ, aug-cc-pVTZ, and 3-21g** basis sets. According to the results of the vertical excited energies and oscillator strengths of these low-lying excited states, bond selectivity is predicted. Subsequently, the minimum energy paths of the first excited singlet state and the third excited state for the dissociation reactions were calculated using the complete active space self-consistent field method with 3-21g** basis set. Good agreement is found between the calculations and experimental data. The relationships of excitations, the electronic structures at Franck-Condon points, and bond selectivity are discussed. (C) 2005 American Institute of Physics.