Semiclassical instanton formulation of Marcus-Levich-Jortner theory.

Abstract

Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects in the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into a subsystem treated quantum-mechanically by Fermi's golden rule and a solvent bath treated by classical Marcus theory. As an extension of this idea, we here present a "reduced" semiclassical instanton theory, which is a multiscale method for simulating quantum tunneling of the subsystem in molecular detail in the presence of a harmonic bath. We demonstrate that instanton theory is typically significantly more accurate than the cumulant expansion or the semiclassical Franck-Condon sum, which can give orders-of-magnitude errors and, in general, do not obey detailed balance. As opposed to MLJ theory, which is based on wavefunctions, instanton theory is based on path integrals and thus does not require solutions of the Schrödinger equation nor even global knowledge of the ground- and excited-state potentials within the subsystem. It can thus be efficiently applied to complex, anharmonic multidimensional subsystems without making further approximations. In addition to predicting accurate rates, instanton theory gives a high level of insight into the reaction mechanism by locating the dominant tunneling pathway as well as providing similar information to MLJ theory on the bath activation energy and the vibrational excitation energies of the subsystem states involved in the reaction.