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American Institute of Physics, The Journal of Chemical Physics, 8(139), p. 084115, 2013

DOI: 10.1063/1.4819076

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Derivation of a true (t → 0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing

Journal article published in 2013 by Stuart C. Althorpe, Timothy J. H. Hele ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

In Paper I [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory (TST) by taking the t → 0+ limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This t → 0+ limit appears to be unique in giving positive-definite Boltzmann statistics, and is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we show that quantum TST (i.e., RPMD-TST) is exact if there is no recrossing (by the real-time quantum dynamics) of the ring-polymer dividing surface, nor of any surface orthogonal to it in the space describing fluctuations in the polymer-bead positions along the reaction coordinate. In practice, this means that RPMD-TST gives a good approximation to the exact quantum rate for direct reactions, provided the temperature is not too far below the cross-over to deep tunnelling. We derive these results by comparing the t → ∞ limit of the ring-polymer flux-side time-correlation function with that of a hybrid flux-side time-correlation function (containing a ring-polymer flux operator and a Miller-Schwarz-Tromp side function), and by representing the resulting ring-polymer momentum integrals as hypercubes. Together with Paper I, the results of this article validate a large number of RPMD calculations of reaction rates.