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Spin‐orbit Coupling and Intersystem Crossing in 4 H ‐Pyran‐4‐thione: CASSCF//TD‐B3LYP Study
Author(s) -
LÜ LingLing,
LIU XinWen,
YUAN Kun,
WANG YongCheng,
WANG HanQing
Publication year - 2007
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200790270
Subject(s) - intersystem crossing , chemistry , phosphorescence , triplet state , atomic physics , hamiltonian (control theory) , spin (aerodynamics) , ground state , spin–orbit interaction , radiative transfer , molecular physics , photochemistry , excited state , singlet state , fluorescence , physics , molecule , quantum mechanics , mathematical optimization , mathematics , organic chemistry , thermodynamics
The intersystem crossing channels of gaseous 4 H ‐pyran‐4‐thione were investigated using the CASSCF//TD‐B3LYP methods and group theory. Using the effective one‐electron spin‐orbit Hamiltonian, the strengths of spin‐orbit coupling were estimated, which plays an essential role in the spin transitions between different spin states. Calculated results show that phosphorescence and non‐radiative decay via intersystem crossing to the S 0 state are concurrent processes occurring at the T 1 state. A rapid depletion of the S 1 state via intersystem crossing to the T 1 state can be mediated by the T 2 state, if spin relaxation is fast within the triplet levels. Our calculated results are in close agreement with experimental observations.