DOI: 10.1063/1.451009. Energy diffusion in many-dimensional Markovian systems: The consequences of competition between inter- and intramolecular vibrational energy transfer

Energy diffusion in many-dimensional Markovian systems: The consequences of competition between inter- and intramolecular vibrational energy transfer

10.1063/1.451009

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We examine the dynamics of barrier crossing using a two-dimensional Langevin equation in the low friction regime. We find that as the friction on the nonreactive mode is increased there is a transition from two-dimensional Markovian dynamics to one-dimensional non-Markovian dynamics resulting in a qualitative change in the behavior of the rate constant as a function of friction. This result supports the conclusion that existing theories which predict rates for energy activation in Markovian and non-Markovian systems have limited ranges of validity and are not as general as had previously been supposed. A method is proposed which analyzes the eigenvalues of the full system and provides a criterion for the validity of the various theories. These ideas are then used to interpret the results of a recent experimental study. In the Appendix we discuss, in some detail, the role of a random force in aiding intramolecular energy transfer.

Bibliography

Straub, J. E., & Berne, B. J. (1986). Energy diffusion in many-dimensional Markovian systems: The consequences of competition between inter- and intramolecular vibrational energy transfer. The Journal of Chemical Physics, 85(5), 2999â3006.

Authors 2

John E. Straub (first)
Bruce J. Berne (additional)

References 47 Referenced 49

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:02 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 12:03 a.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 9:21 p.m.)
Issued	38 years, 11 months ago (Sept. 1, 1986)
Published	38 years, 11 months ago (Sept. 1, 1986)
Published Print	38 years, 11 months ago (Sept. 1, 1986)

Funders 0

None

BibTeX

@article{Straub_1986, title={Energy diffusion in many-dimensional Markovian systems: The consequences of competition between inter- and intramolecular vibrational energy transfer}, volume={85}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.451009}, DOI={10.1063/1.451009}, number={5}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Straub, John E. and Berne, Bruce J.}, year={1986}, month=sep, pages={2999–3006} }

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