An alternative derivation of ring-polymer molecular dynamics transition-state theory.

Abstract

In a previous article [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)], we showed that the t → 0+ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the t → 0+ limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RMPD-TST) is a t → 0+ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum t → 0+ limit and claimed that it gives instead the centroid-density approximation. Here we show that the t → 0+ limit derived by Jang and Voth is in fact RPMD-TST.