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American Institute of Physics, The Journal of Chemical Physics, 17(144), p. 174107, 2016

DOI: 10.1063/1.4947589

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

Journal article published in 2016 by Timothy J. H. Hele ORCID, Stuart C. Althorpe ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by the American Institute of Physics. ; In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the transition-state-theory (t ? 0_+) limit of ring-polymer molecular dynamics rate-theory (RPMD-TST) is also the t ? 0_+ limit of a new type of quantum ux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD-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. ; We acknowledge funding from the UK Science and Engineering Research Council. TJHH also acknowledges a Research Fellowship from Jesus College, Cambridge.