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Spin-Orbit Ab Initio Investigation of the Ultraviolet Photolysis of Diiodomethane

✍ Scribed by Ya-Jun Liu; Luca De Vico; Roland Lindh; Wei-Hai Fang

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
269 KB
Volume
8
Category
Article
ISSN
1439-4235

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✦ Synopsis

Abstract

The UV photodissociation (<5 eV) of diiodomethane (CH~2~I~2~) is investigated by spin‐orbit ab initio 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~I~2~ and CH~2~II lead to geminate‐radical products, CH~2~I^.^+I(^2^P~3/2~) or CH~2~I^.^+ I*(^2^P~1/2~). The recombination process from CH~2~II to CH~2~I~2~ is explained by an isomerization process and a secondary photodissociation reaction of CH~2~II. Finally, the study reveals that spin‐orbits effects are significant in the quantitative analysis of the electronic spectrum of the CH~2~II species.

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