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.

10 pages, 1 figure. Typographical errors corrected, references updated and added

References in corpus (3)

• Derivation of a true (t->0+) quantum transition-state theory. Part I: Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory
• Quantum effects in the diffusion of hydrogen on Ru(0001)
• Derivation of a true (t->0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing

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