Theoretical study of the effect of the intermolecular spin-orbit interaction in the collision-induced intersystem crossing of S-1 state glyoxal by Ar

Citation
T. Nakajima et S. Kato, Theoretical study of the effect of the intermolecular spin-orbit interaction in the collision-induced intersystem crossing of S-1 state glyoxal by Ar, J PHYS CH A, 105(47), 2001, pp. 10657-10663
Citations number
55
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
1089-5639 → ACNP
Volume
105
Issue
47
Year of publication
2001
Pages
10657 - 10663
Database
ISI
SICI code
1089-5639(20011129)105:47<10657:TSOTEO>2.0.ZU;2-I
Abstract
The intersystem crossing from S-1 to T-1 in glyoxal induced by the collisio n of Ar has been studied theoretically. In particular, we have focused on t he effects of the intermolecular spin-orbit interaction, which was not cons idered important in this process. The interaction potential of S-1 in the g lyoxal and Ar system was carried out by the CASSCF method. Further, the int eraction potential of T-1 and the spin-orbit interaction, which is represen ted by the Breit-Pauli Hamiltonian, between S-1 and T-1 were calculated by the full-CI method with the same active spaces and molecular orbitals as th ose of the CASSCF calculations for S-1. Using these calculation results, th e semiclassical dynamics calculations were employed to estimate the transit ion cross sections and rate constants. It is found that the intermolecular spin-orbit interaction largely amplifies the transition probabilities and t he relaxation on the T-1 state is indispensable to describing the dynamics in this intersystem crossing.