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Time-Resolved and Fourier Transform Epr Studies of Type i pHotochemical Reaction. Direct Determination of Kinetic Parameters of C-c bOnd Cleavage

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Continuous wave time-resolved EPR (CW-TREPR) and pulsed Fourier transform EPR (FT-EPR) experiments with a resolution of ~10 ns were carried out to investigate the Type I photocleavage. A two-pulse echo detection method was used to eliminate the dead-time problem in the FID measurements. An analysis of the buildup kinetics of the FT-EPR signal intensity due to t-butyl radicals provided the rates of the α-cleavage of t-butylphenyl ketone at various temperatures. We obtained two kinetic parameters at low and high temperatures which correspond to the non-radiative decay rate of the excited triplet state of the ketone and the rate of the Type I photocleavage, respectively.

Affiliations: 1: Institute for Chemical Reaction Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980, JAPAN


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