Comparison of rate theories for generalized Langevin dynamics

Susan C. Tucker, Mark Tuckerman, Bruce J. Berne, Eli Pollak

Research output: Contribution to journalArticle

Abstract

Rate constants evaluated from (1) the energy-loss turnover theory of Pollak, Grabert, and Hänggi (PGH), (2) the Grote-Hynes extension of Kramers theory (GH), and (3) the microcanonical variational transition state theory for dissipative systems of Tucker and Pollak (μVTST) are compared with rate constants determined from direct computer simulations of generalized Langevin dynamics. The comparisons are made for a cubic oscillator under the influence of a slow bath characterized by a Gaussian friction kernel. In the μVTST calculations, which are based on an effective two degree of freedom, Hamiltonian, barrier crossing due to energy transfer from the bath to the effective Hamiltonian is neglected. This neglect is significant only at very strong coupling, where it causes the μVTST results to drop below the simulation results. Both GH and μVTST theories fail (as expected) in the energy diffusion regime, while PGH theory is only moderately successful. The μVTST results agree extremely well with the simulation results in the spatial diffusion regime, providing a significant improvement over the GH results at intermediate coupling strengths and over the PGH results at strong coupling strengths. This improvement is a result of nonlinear effects which are included in the μVTST approach but neglected in the PGH and GH theories.

Original languageEnglish (US)
Pages (from-to)5809-5826
Number of pages18
JournalJournal of Chemical Physics
Volume95
Issue number8
StatePublished - 1991

Fingerprint

Hamiltonians
Rate constants
baths
Energy transfer
Energy dissipation
Friction
Computer simulation
friction
simulation
degrees of freedom
computerized simulation
energy dissipation
energy transfer
oscillators
causes
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Tucker, S. C., Tuckerman, M., Berne, B. J., & Pollak, E. (1991). Comparison of rate theories for generalized Langevin dynamics. Journal of Chemical Physics, 95(8), 5809-5826.

Comparison of rate theories for generalized Langevin dynamics. / Tucker, Susan C.; Tuckerman, Mark; Berne, Bruce J.; Pollak, Eli.

In: Journal of Chemical Physics, Vol. 95, No. 8, 1991, p. 5809-5826.

Research output: Contribution to journalArticle

Tucker, SC, Tuckerman, M, Berne, BJ & Pollak, E 1991, 'Comparison of rate theories for generalized Langevin dynamics', Journal of Chemical Physics, vol. 95, no. 8, pp. 5809-5826.
Tucker, Susan C. ; Tuckerman, Mark ; Berne, Bruce J. ; Pollak, Eli. / Comparison of rate theories for generalized Langevin dynamics. In: Journal of Chemical Physics. 1991 ; Vol. 95, No. 8. pp. 5809-5826.
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