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The role of rotational relaxation in the intersystem crossing between a triplet and a singlet electronic state
Author(s) -
Rashev Svetoslav,
Moule David C.,
Judge Richard H.
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22766
Subject(s) - intersystem crossing , singlet state , chemistry , wave function , relaxation (psychology) , atomic physics , triplet state , population , spin (aerodynamics) , molecular physics , physics , excited state , thermodynamics , psychology , social psychology , demography , sociology
A calculation of the rate of ISC (intersystem crossing) relaxation at 0 K requires a knowledge of the spin–orbit coupling and the vibrational overlap integrals (Franck‐Condon factors) between the T 1 and S 0 states. At elevated temperatures, the population of the rotational states needs to be taken into account through the overlap of the rotational wavefunctions between the interacting T 1 /S 0 electronic states. Here, we discuss the effect of the ISC singlet–triplet selection rules on the number and magnitude of the rotational overlap factors for the J = 0, 5, and 10 rotational levels of thiophosgene, Cl 2 CS. Of equal importance is the influence of the spin–spin and spin‐rotation coupling on the rotational fragmentation factors and the ISC survival probability. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011