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• W2147758478 abstract "A large solvent polarity effect on the rate of singlet to triplet intersystem crossing ( k ST ) has been observed in the carbenes, diphenylcarbene (DPC) and dicycloheptadienylidene (DCHD). It is found that both k ST and the energy splitting (Δ E ST ) separtaing the singlet and triplet states decrease as the solvent polarity increases for the aromatic carbenes. This “inverse” gap effect, i.e. the time for intersystem crossing decreases with increasing energy gap, is explained by an off-resonance intersystem crossing from the singlet to a sparse triplet vibronic manifold characteristic of a small energy gap. The trend in Δ E ST , which is proposed to be responsible for the variation in k ST for DPC, DCHD and structurally related aromatic carbenes, is suggested to arise from the variation in the bond angle of the central methylene carbon atom." @default.
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• W2147758478 date "1984-10-01" @default.
• W2147758478 modified "2023-09-26" @default.
• W2147758478 title "Picosecond laser studies on the effect of structure and environment on intersystem crossing in aromatic carbenes" @default.
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• W2147758478 doi "https://doi.org/10.1016/0009-2614(84)87083-9" @default.
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