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

Abstract

In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the $t\to 0_{+}$ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the $t\to 0_{+}$ 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 (RPMD-TST) is a $t\to 0_{+}$ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum $t\to 0_{+}$ limit, and claimed that it gives instead the centroid-density approximation. Here we show that the $t\to 0_{+}$ limit derived by Jang and Voth is in fact RPMD-TST.

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• Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Theory and Practical Applications
• Thermal quantum time-correlation functions from classical-like dynamics
• Non-uniqueness of quantum transition state theory and general dividing surfaces in the path integral space
• Identification of the invariant manifolds of the LiCN molecule using Lagrangian descriptors
• On the electronic path integral normal modes of the Meyer-Miller-Stock-Thoss representation of nonadiabatic dynamics