Authors

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.