Dynamics of bimolecular reactions of vibrationally highly excited molecules

Quasiclassical trajectory studies

Erika Bene, G. Lendvay, György Póta

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Excitation functions from quasiclassical trajectory calculations on the H + H2O→OH + H2, + HF → F + H2, and H + H′F → H′ + HF reactions indicate a different behavior at low and high vibrational excitation of the breaking bond. When the reactant tri- or diatomic molecule is in vibrational ground state or in a low vibrationally excited state, all these reactions are activated; i.e., there is a nonzero threshold energy below which there is no reaction. In contrast, at high-stretch excited-states capture-type behavior is observed; i.e., with decreasing translational energy the reactive cross-section diverges. The latter induces extreme vibrational enhancement of the thermal rate consistent with the experiments. The results indicate that the speed-up Observed at high vibrational excitation is beyond the applicability of Polanyi's rules in their common form; instead, it can be interpreted in terms of an attractive potential acting on the attacking H atom when it approaches the reactant with a stretched X-H bond.

Original languageEnglish
Pages (from-to)8336-8340
Number of pages5
JournalJournal of Physical Chemistry A
Volume109
Issue number37
DOIs
Publication statusPublished - Sep 22 2005

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Excited states
Trajectories
trajectories
Molecules
Ground state
excitation
molecules
Atoms
triatomic molecules
diatomic molecules
Experiments
ground state
thresholds
energy
augmentation
cross sections
atoms
Hot Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Dynamics of bimolecular reactions of vibrationally highly excited molecules : Quasiclassical trajectory studies. / Bene, Erika; Lendvay, G.; Póta, György.

In: Journal of Physical Chemistry A, Vol. 109, No. 37, 22.09.2005, p. 8336-8340.

Research output: Contribution to journalArticle

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