An alternative derivation of ring-polymer molecular dynamics transition-state theory
Chemical Physics
2016-05-06 v2 Quantum Physics
Abstract
In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the 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 (RPMD-TST) is a quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum limit, and claimed that it gives instead the centroid-density approximation. Here we show that the limit derived by Jang and Voth is in fact RPMD-TST.
Cite
@article{arxiv.1603.07966,
title = {An alternative derivation of ring-polymer molecular dynamics transition-state theory},
author = {Timothy J. H. Hele and Stuart C. Althorpe},
journal= {arXiv preprint arXiv:1603.07966},
year = {2016}
}