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On the uniqueness of t->0+ quantum transition-state theory
- Publication Year :
- 2013
-
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.<br />Comment: 10 pages, 1 figure. Typographical errors corrected, references updated and added
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....6d91d4e7bf35409db6bd1d16e3b88309