Spin-orbit ab initio investigation of the ultraviolet photolysis of diiodomethane
- Liu, Ya-Jun
- De Vico, Luca
- Lindh, Roland
- Fang, Wei-Hai
DOIAbstract
The UV photodissociation (<5 eV) of diiodomethane (CH(2)l(2)) is investigated by spin-orbit ab inito calculations. The experimentally observed photodissociation channels in the gas and condensed phases are clearly assigned by multi-state second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space-state interaction potential energy curves. The calculated results indicate that the fast dissociations of the first two singlet states of CH(2)l(2) and CH(2)l-l lead to geminate-radical products, CH(2)l(+) +l(P-2(3/2)) or CH(2)l(+) + l*(P-2(1/2)). The recombination process from CH(2)l-l to CH(2)l(2) is explained by an isomerazation process and a secondary photodissociation reaction ...
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