An alternative derivation of ring-polymer molecular dynamics transition-state theory
In a previous article [T. J. H. Hele and S. C. Althorpe, J. Chem. Phys. 138, 084108 (2013)], we showed that the t → 0{sub +} limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the t → 0{sub +} limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RMPD-TST) is a t → 0{sub +} quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum t → 0{sub +} limit and claimed that it gives instead the centroid-density approximation. Here we show that the t → 0{sub +} limit derived by Jang and Voth is in fact RPMD-TST.
- OSTI ID:
- 22657954
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 17; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Can quantum transition state theory be defined as an exact t = 0+ limit?
Dimension-free path-integral molecular dynamics without preconditioning