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

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 (equivalent to 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 RPMDTST. (c) 2013 AIP Publishing LLC.