Reflection on medium effects on photochemical reactivity |
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Authors: | Liu Robert S H Hammond George S |
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Affiliation: | Department of Chemistry, University of Hawaii, 2545 The Mall, Honolulu, Hawaii 96822, USA. rliu@gold.chem.hawaii.edu |
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Abstract: | In reexamining medium effects on photochemical reactions, we have emphasized those on unequilibrated excited species such as the Franck-Condon species. Despite recent advances in femtochemistry, such a discussion in molecular photochemistry is uncommon, and the problem remains challenging on account of the extremely short-lived excited species. However, in such cases, a small perturbation resulting from, for example, weak guest-host interactions could turn into a determining factor in dictating the course of a photochemical channel of deactivation. Examples of medium-directed diabatic processes have been examined with this idea in mind. A modified view on rhodopsin photoisomerization is presented along with the consideration that confinement does not necessarily lead to inhibition of reactions of the trapped substrate. |
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