title: 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.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Timothy J H
authors.initials: TJ
authors.lastname: Hele
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Stuart C
authors.initials: SC
authors.lastname: Althorpe