Published in

American Institute of Physics, The Journal of Chemical Physics, 8(139), p. 084116, 2013

DOI: 10.1063/1.4819077

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On the uniqueness of t → 0+ quantum transition-state theory

Journal article published in 2013 by Timothy J. H. Hele ORCID, Stuart C. Althorpe
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

It was shown recently that there exists a true quantum transition-state theory (QTST) corresponding to the t → 0+ limit of a (new form of) quantum flux-side time-correlation function. Remarkably, this QTST is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we provide evidence which suggests very strongly that this QTST (≡ RPMD-TST) is unique, in the sense that the t → 0+ limit of any other flux-side time-correlation function gives either non-positive-definite quantum statistics or zero. We introduce a generalized flux-side time-correlation function which includes all other (known) flux-side time-correlation functions as special limiting cases. We find that the only non-zero t → 0+ limit of this function that contains positive-definite quantum statistics is RPMD-TST.