ON THE TEMPERATURE DEPENDENCE OF RADIATIONLESS TRANSITIONS

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1970

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Ohio State University

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Temperature dependent contributions of the rate constant resulting from a) accepting modes, b) promoting modes, c) medium effects are discussed. For the low temperature region the rate constant is brought in the conventional form k(T)=k(T=0)+{Ae}^{-{E_{o}}/{kT}} The dependence of the activation energy $E_{a}$ and the preexponential factor A upon temperature deuteration and the viscosity of the medium are discussed and compared with $experiments.^{1}$ It is found that the medium effects play a dominant role at low temperatures. The time dependent correlation function for the rate constant is computed to demonstrate these effects.

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$^{1}$G.F. Hatch, M.D. Erlitz, and G.C. Nieman, in E. C. Lim. ``Molecular Luminescence"""", W.A. Benjarman, New York, N. Y., 1969. p. 21 ff., Ingo H. Leubner, J. Phys. Chem. 74,77 (1970).""
Author Institution: Department of Chemistry, Northwestern University

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