DOI: 10.1063/1.435826. Threshold behavior of endoergic bimolecular reactions: A statistical phase space approach

Threshold behavior of endoergic bimolecular reactions: A statistical phase space approach

10.1063/1.435826

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A statistical phase space theory is developed for threshold and near threshold behavior of endoergic bimolecular reactions. A simple, exact threshold law for the cross section is derived for collisions between atomic, diatomic, or polyatomic species in all combinations. An approximate expression is derived for the cross section that is valid between threshold and about 0.5 eV above threshold. Analytical expressions are obtained in both cases that allow cross section versus energy curves to be generated using only hand-held electronic calculators. The utility of the theory is demonstrated by comparing the theoretical predictions with experiment for the reactions C+⋅ (D2,D⋅)CD+, H2O+⋅ (H2,OH⋅)H+3, and D3O+(D2,D2O)D+3. The first reaction behaves statistically in the threshold region while the second and third do not. A correlation is made between the statistical behavior of the reaction and the stability of the collision complex: The intermediate CD+2⋅ is very stable (98 kcal/mole) while the ions H4O+⋅ and D5O+ are unstable. The utility of the approximate threshold theory for exploring the molecular origins for the cross-sectional changes with energy is emphasized.

Bibliography

Chesnavich, W. J., & Bowers, M. T. (1978). Threshold behavior of endoergic bimolecular reactions: A statistical phase space approach. The Journal of Chemical Physics, 68(3), 901â910.

Authors 2

W. J. Chesnavich (first)
M. T. Bowers (additional)

References 21 Referenced 42

{'key': '2024020916040794200_r1'}
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10.1063/1.430398 / J. Chem. Phys. (1975)
{'key': '2024020916040794200_r5', 'first-page': '135', 'volume': '1', 'year': '1965', 'journal-title': 'Teor. Eksp. Khim.'} / Teor. Eksp. Khim. (1965)
{'key': '2024020916040794200_r5a', 'first-page': '83', 'volume': '1', 'year': '1975', 'journal-title': 'Theor. Exp. Chem.'} / Theor. Exp. Chem. (1975)
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{'key': '2024020916040794200_r8'}
{'key': '2024020916040794200_r9'}
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{'key': '2024020916040794200_r12'}
{'key': '2024020916040794200_r13', 'first-page': '340', 'volume': '71', 'year': '1971', 'journal-title': 'Chem. Rev.'} / Chem. Rev. (1971)
{'key': '2024020916040794200_r14'}
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Dates

Type	When
Created	22 years, 5 months ago (Feb. 27, 2003, 5:38 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 12:22 p.m.)
Indexed	1 year, 1 month ago (July 12, 2024, 5:52 p.m.)
Issued	47 years, 6 months ago (Feb. 1, 1978)
Published	47 years, 6 months ago (Feb. 1, 1978)
Published Print	47 years, 6 months ago (Feb. 1, 1978)

Funders 0

None

BibTeX

@article{Chesnavich_1978, title={Threshold behavior of endoergic bimolecular reactions: A statistical phase space approach}, volume={68}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.435826}, DOI={10.1063/1.435826}, number={3}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Chesnavich, W. J. and Bowers, M. T.}, year={1978}, month=feb, pages={901–910} }

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