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The intersystem crossing channels of gaseous 4H-pyran-4-thione were investigated using the CASSCF//TD-B3LYP methods and group theory. Calculated results show that phosphorescence and nonradiative decay via intersystem crossing to the S 0 state are simultaneous processes occurring at the T 1 state. The spin–orbit coupling constant in the S 0 /T 1 intersection is large,...
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