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Photochemistry with thermal versus optical excess energy: Ultrafast cycloreversion of indolylfulgides and indolylfulgimides

Paper ID Volume ID Publish Year Pages File Format Full-Text
28066 44058 2009 8 PDF Available
Title
Photochemistry with thermal versus optical excess energy: Ultrafast cycloreversion of indolylfulgides and indolylfulgimides
Abstract

The dependence of the pericyclic ring-opening reaction of indolylfulgides and indolylfulgimides on excess energy is investigated by quantum efficiency measurements and by ultrafast spectroscopy. The ring-opening reaction shows a pronounced improvement of reaction efficiency up to a factor of 6, when excess energy is available either by increasing the temperature or by exciting the molecules above the 0–0-transition. Ultrafast spectroscopy allows to deduce time constants for the ring-opening reaction and leads to a theoretical model, where the redistribution of excess energy among different vibrational modes is considered. The analysis shows that excess energy supplied by optical excitation accelerates the ring-opening reaction less efficiently than thermal energy. Apparently vibrational relaxation from highly excited modes to modes promoting the ring-opening reaction is not completed within the ∼10 ps duration of the ring-opening reaction.

Keywords
Fulgide; Fulgimide; Photochromism; Kasha–Vavilov rule; Arrhenius
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Photochemistry with thermal versus optical excess energy: Ultrafast cycloreversion of indolylfulgides and indolylfulgimides
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 207, Issues 2–3, 25 September 2009, Pages 209–216
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
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Don't Miss Today's Special Offer
Price was $35.95
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Price after discount Only $4.95
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