Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations

Abstract

We describe a path-integral molecular dynamics implementation of our recently developed golden-rule quantum transition-state theory (GR-QTST). The method is applied to compute the reaction rate in various models of electron transfer and benchmarked against exact results. We demonstrate that for systems exhibiting two or more transition states, rates computed using Wolynes theory [P. G. Wolynes, J.\ Chem.\ Phys.\ 87, 6559 (1987)] can be overestimated by orders of magnitude, whereas the GR-QTST predictions are numerically accurate. This is the case both at low temperature, where nuclear tunneling makes a considerable contribution, and also in the classical limit, where only GR-QTST rigorously tends to the correct result. Analysis shows that the saddle-point approximation employed by Wolynes theory is not valid in this case, which results in predictions of unphysical reaction pathways, whilst the energy constraint employed by GR-QTST resolves this problem. The GR-QTST method is also seen to give accurate results for a strongly anharmonic system by sampling configurations around the instanton pathway without making the semiclassical approximation. These promising results indicate that the GR-QTST method could be an efficient and accurate approach for simulating electron-transfer reactions in complex molecular systems.