DOI: 10.1063/1.475756. Activated chemistry in the presence of a strongly symmetrically coupled vibration

Activated chemistry in the presence of a strongly symmetrically coupled vibration

10.1063/1.475756

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

In the gas phase, tunneling reaction rates can be significantly enhanced if the reaction coordinate is symmetrically coupled to a harmonic oscillation, as has been emphasized by Benderskii and co-workers [Adv. Chem. Phys. 88, 1 (1994)]. This is due to the fact that the symmetric coupling leads to modulation of the barrier height. Similar effects have been observed in reactions in model condensed phase studies, as in the Hamiltonians that have been studied by Borgis and Hynes [J. Chem. Phys. 94, 3619 (1991)] and Suarez and Silbey [J. Chem. Phys. 94, 4809 (1991)]. All of these works assume that tunneling proceeds from the ground state. In this paper, we use the exponential resummation technique that we used in our recent work on the quantum Kramers problem, to study the case when there can be excitations to higher states and activated transmission over a barrier. We present a general methodology to exactly include direct coupling between the reaction coordinate and the symmetrically coupled promoting vibration and find that the rate of reactions in condensed phases is enhanced as in the case of tunneling from the ground state. This effect, however, is strongly modulated by loss of coherence induced by the condensed phase environment.

Bibliography

Antoniou, D., & Schwartz, S. D. (1998). Activated chemistry in the presence of a strongly symmetrically coupled vibration. The Journal of Chemical Physics, 108(9), 3620â3625.

Authors 2

Dimitri Antoniou (first)
Steven D. Schwartz (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:16 a.m.)
Deposited	1 year, 6 months ago (Feb. 7, 2024, 4:07 p.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 6:46 p.m.)
Issued	27 years, 5 months ago (March 1, 1998)
Published	27 years, 5 months ago (March 1, 1998)
Published Print	27 years, 5 months ago (March 1, 1998)

Funders 0

None

BibTeX

@article{Antoniou_1998, title={Activated chemistry in the presence of a strongly symmetrically coupled vibration}, volume={108}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.475756}, DOI={10.1063/1.475756}, number={9}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Antoniou, Dimitri and Schwartz, Steven D.}, year={1998}, month=mar, pages={3620–3625} }

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