TY - JOUR

T1 - Some theoretical results for the photochemical decomposition of large molecules

AU - Kay, Kenneth G.

AU - Rice, Stuabt A.

PY - 1972

Y1 - 1972

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0007118899&partnerID=8YFLogxK

U2 - 10.1063/1.1678717

DO - 10.1063/1.1678717

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AN - SCOPUS:0007118899

SN - 0021-9606

VL - 57

SP - 3041

EP - 3047

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 8

ER -