Quantum theory of inner sphere electron transfer reactions

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Abstract
This paper reports a theory of inner sphere electron transfer reactions for which, in addition to the electron transfer, there is bond formation and/or destruction. We assume that steps in the reaction sequence which involve bond synthesis take place in intermediate activated complex states. The problem of inner sphere electron transfer is large and complicated. The theory described applies to one aspect of the problem, namely, the dynamics of simultaneous electron transfer and bond break in the transition state complex. However, we assume the intermediate complex exists in steady state equilibrium with the reactants. The theory developed in this paper reveals features important in the unimolecular decay of the transition state. In particular, the importance of the Franck-Condon restrictions on bond forming and breaking steps is demonstrated.

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