title: On the uniqueness of t → 0+ quantum transition-state theory.
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.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors.forename: Timothy J H
authors.initials: TJ
authors.lastname: Hele
authors.forename: Stuart C
authors.initials: SC
authors.lastname: Althorpe