Marcus Theory and The Condon Approximation Revisited II: The Horror of Triplet Energy Transfer

We investigate the applicability of the Condon approximation (i.e. the notion that the diabatic coupling is invariant to geometry) in the context of both electron transfer (ET) and triplet energy transfer (TET) and compare the two cases. Although it is well appreciated that diabatic couplings usually arise from the interactions of electronic wavefunction tails, we show that ET tails are very different from TET tails. Using a simple model problem, our analysis explains in detail why the rates of TET decays with twice the rate of ET, while also leading to the hypothesis that the smaller diabatic couplings found for TET (versus ET) should imply more sensitivity to non-Condon fluctuations. As an example, for the classic sets of molecules investigated by Closs, we show that the Condon approximation is indeed less applicable for TET than for ET.