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Equivalence of the radical recombination rate theories of Waite and Szabo

✍ Scribed by Younjoon Jung; Sangyoub Lee

Publisher: Elsevier Science
Year: 1994
Tongue: English
Weight: 716 KB
Volume: 231
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(94)01282-2

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✦ Synopsis

Recombination reactions of radicals generated by photolysis are often analyzed by considering the reactive dynamics of an isolated geminate pair. However, when the concentration of photodissociated radical pairs is high, the recombination of nongeminate radicals should also be taken into account. This aspect of recombination reactions between photolyzed radicals was first considered by Waite using the nonequilibrium distribution function formalism. We present a more straightforward derivation of Waite's rate equation. A generalization is made to include the case where one of the reactant species is present in excess of the other. In the pseudo-first-order case, the generalized rate equation yields the same analytic expression for the survival probability of photodissociated radicals as recently derived by Szabo.

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