An alternative derivation of ring-polymer molecular dynamics transition-state theory
Journal of Chemical Physics
American Institute of Physics
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Hele, T., & Althorpe, S. (2016). An alternative derivation of ring-polymer molecular dynamics transition-state theory. Journal of Chemical Physics https://www.repository.cam.ac.uk/handle/1810/255759
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.
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