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Solvent Cage Effects: A Comparison of Geminate and Nongeminate Radical Cage Pair Combination Efficiencies
Justin T Barry1, David R Tyler1
1Department of Chemistry and Biochemistry, 1253 University of Oregon, Eugene, Oregon 97403, United States.
Abstract:
This study measured and compared the combination efficiencies (FcP) of geminate radical cage pairs to nongeminate (collisional) radical cage pairs (Fc'). For the [Cp'(CO)3Mo·, ·Mo(CO)3Cp'] radical cage pair, Fc' was found to be smaller than FcP in solutions having the same viscosity. It is proposed that the difference in FcP and Fc' arises because the radicals in the collisional cage pair are less likely to have the correct orbital orientation for radical-radical combination to occur, whereas photochemically generated geminate cage pairs are more likely to have the correct orbital orientation. As predicted, FcP and Fc' both increase when the microviscosity of a solution increases.
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