Journal
CHEMPHYSCHEM
Volume 8, Issue 6, Pages 890-898Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.200600737
Keywords
ab initio calculations; absorption; isomerization; photochemistry; reaction mechanisms
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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 of CH(2)l-l. Finally, the study reveals that spin-orbits effects are sifnificant in the quantitative analysis of the electronic spectrum of the CH(2)l-l species.
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