An alternative derivation of ring-polymer molecular dynamics transition-state theory.
Hele, Timothy JH
Althorpe, Stuart C
J Chem Phys
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Hele, T. J., & Althorpe, S. C. (2016). An alternative derivation of ring-polymer molecular dynamics transition-state theory.. J Chem Phys https://doi.org/10.1063/1.4947589
In a previous article [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)], we showed that the t → 0+ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the t → 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 (RMPD-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.
External DOI: https://doi.org/10.1063/1.4947589
This record's URL: https://www.repository.cam.ac.uk/handle/1810/255759
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Licence URL: http://creativecommons.org/licenses/by-nc/4.0/
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