Some theoretical results for the photochemical decomposition of large molecules

Kenneth G. Kay, Stuabt A. Rice

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The expressions describing photochemical dissociation derived by Rice, McLaughlin, and Jortner are evaluated analytically for molecules satisfying Γ≫(l+r) and for times t≪h/ε, where T is the width of the initial state due to interaction with an intermediate manifold, ε is the level spacing of the manifold, and r is essentially the ratio of the manifold level widths to ε. Excitation is found to decay exponentially from the initial state with rate Γ/[ (1+r)h]. In contrast to the behavior originally perdicted, the decay is found to be nonsequential, and a constant ratio, equal to r, is maintained between the populations of the continuum and the manifold. The results should be applicable to large molecules having a single decomposition mode.

Original languageEnglish
Pages (from-to)3041-3047
Number of pages7
JournalJournal of Chemical Physics
Issue number8
StatePublished - 1972
Externally publishedYes


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