Quantized time correlation function approach to non-adiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Borgis, Daniel and Rossky, Peter and Turi, László (2006) Quantized time correlation function approach to non-adiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol. Journal of Chemical Physics, 125 (6). 064501. ISSN ISSN 1089-7690

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Abstract

A new, alternative form of the golden rule formula defining the non-adiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the non-adiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via MD simulations. The formalism is applied to the problem of the non-adiabatic relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvent, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated non-adiabatic coupling.

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