Activated chemistry in the presence of a strongly symmetrically coupled vibration

Dimitri Antoniou, Steven D Schwartz

Research output: Contribution to journalArticle

52 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)3620-3625
Number of pages6
JournalThe Journal of Chemical Physics
Volume108
Issue number9
StatePublished - Mar 1 1998
Externally publishedYes

Fingerprint

Ground state
chemistry
Hamiltonians
vibration
Reaction rates
Gases
Modulation
harmonic oscillation
ground state
reaction kinetics
methodology
vapor phases
modulation
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Activated chemistry in the presence of a strongly symmetrically coupled vibration. / Antoniou, Dimitri; Schwartz, Steven D.

In: The Journal of Chemical Physics, Vol. 108, No. 9, 01.03.1998, p. 3620-3625.

Research output: Contribution to journalArticle

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