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Photoisomerization through a “funnel” in polar and non-polar solvents

✍ Scribed by Z. Smedartchina

Publisher
Elsevier Science
Year
1985
Tongue
English
Weight
475 KB
Volume
113
Category
Article
ISSN
0009-2614

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✦ Synopsis

Fast radiationless deactivation Se -+ S,-, of a photoexcited state through a "funnel" is discussed. Thz experimental rates of such transitions cannot be ehplained in general by a one-dimensional model considem only the an&e of isomerizatIon. Inclusion of the full number of degrees of freedom Ia& *-a Go a multidimensional intersection of the adiabatic potential energy surfaces U, and U. in the region of the "funnel" where non-adiabatic interactions are strong and cause a fast electronic transition S, -+ So. The rate constant of the tiomenzation reaction is found to be strongly related to the rate of rotational relaxation in the solvent and relsxation of the solvent orientational polarization.

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