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Spin–Orbit Ab Initio Investigation of the Photolysis of Bromoiodomethane
Author(s) -
Liu YaJun,
Ajitha Devarajan,
Krogh Jesper Wisborg,
Tarnovsky Alexander N.,
Lindh Roland
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500654
Subject(s) - photodissociation , ab initio , ab initio quantum chemistry methods , spin (aerodynamics) , computational chemistry , orbit (dynamics) , atomic physics , chemistry , chemical physics , materials science , physics , photochemistry , molecule , thermodynamics , organic chemistry , aerospace engineering , engineering
10.1002/cphc.200500654.abs 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.