Effects of tunnelling and asymmetry for system-bath models of electron transfer

Abstract

We apply the newly derived nonadiabatic golden-rule instanton theory to asymmetric models describing electron-transfer in solution. The models go beyond the usual spin-boson description and have anharmonic free-energy surfaces with different values for the reactant and product reorganization energies. The instanton method gives an excellent description of the behaviour of the rate constant with respect to asymmetry for the whole range studied. We derive a general formula for an asymmetric version of Marcus theory based on the classical limit of the instanton and find that this gives significant corrections to the standard Marcus theory. A scheme is given to compute this rate based only on equilibrium simulations. We also compare the rate constants obtained by the instanton method with its classical limit to study the effect of tunnelling and other quantum nuclear effects. These quantum effects can increase the rate constant by orders of magnitude.

arXiv comment10 pages, 3 figures

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Cited by in corpus (7)

• Instanton formulation of Fermi's golden rule in the Marcus inverted regime
• Semiclassical instanton formulation of Marcus-Levich-Jortner theory
• Nonadiabatic instanton rate theory beyond the golden-rule limit
• Nonadiabatic quantum transition-state theory in the golden-rule limit. I. Theory and application to model systems
• Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations
• Confirming the role of nuclear tunnelling in aqueous ferrous-ferric electron transfer
• Revisiting nuclear tunnelling in the aqueous ferrous-ferric electron transfer