DOI: 10.1063/1.431444. Path integral representation of the reaction rate constant in quantum mechanical transition state theory

Path integral representation of the reaction rate constant in quantum mechanical transition state theory

10.1063/1.431444

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Feynman’s path integral representation of the Boltzmann operator e−βH is used to express the rate constant of a recently formulated quantum mechanical version of transition state theory. By evaluating the path integral in two separate stages, one is able to interpret the result as a generalization of a model suggested several years ago by Johnston and Rapp for handling the nonseparable aspect of tunneling in transition state theory. A Fourier series expansion of the path integral is also developed, and this approach has promise for direct numerical evaluation of the quantum rate expression.

Bibliography

Miller, W. H. (1975). Path integral representation of the reaction rate constant in quantum mechanical transition state theory. The Journal of Chemical Physics, 63(3), 1166â1172.

Authors 1

William H. Miller (first)

References 22 Referenced 84

10.1063/1.1682181 / J. Chem. Phys. (1974)
10.1063/1.430676 / J. Chem. Phys. (1975)
{'key': '2024020913094349300_r3'}
10.1016/0009-2614(74)80293-9 / Chem. Phys. Lett. (1974)
10.1039/tf9383400029 / Trans. Faraday Soc. (1938)
10.1016/0009-2614(71)85049-2 / Chem. Phys. Lett. (1971)
10.1039/tf9383400041 / Trans. Faraday Soc. (1938)
{'key': '2024020913094349300_r8'}
10.1103/PhysRev.181.166 / Phys. Rev. (1969)
{'key': '2024020913094349300_r10', 'first-page': '69', 'volume': '25', 'year': '1974', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1974)
10.1021/ja01462a001 / J. Am. Chem. Soc. (1961)
{'key': '2024020913094349300_r11a'}
10.1007/BF02055756 / Z. Phys. (1927)
10.1073/pnas.18.11.674 / Proc. Natl. Acad. Sci. (U.S.) (1932)
{'key': '2024020913094349300_r13'}
10.1103/PhysRev.181.174 / Phys. Rev. (1969)
{'key': '2024020913094349300_r15'}
{'key': '2024020913094349300_r16'}
{'key': '2024020913094349300_r17'}
{'key': '2024020913094349300_r18'}
{'key': '2024020913094349300_r19'}
10.1103/RevModPhys.38.483 / Rev. Mod. Phys. (1966)

Dates

Type	When
Created	22 years, 6 months ago (Feb. 27, 2003, 3:57 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 8:58 a.m.)
Indexed	2 months, 3 weeks ago (June 4, 2025, 6:05 a.m.)
Issued	50 years ago (Aug. 1, 1975)
Published	50 years ago (Aug. 1, 1975)
Published Print	50 years ago (Aug. 1, 1975)

Funders 0

None

BibTeX

@article{Miller_1975, title={Path integral representation of the reaction rate constant in quantum mechanical transition state theory}, volume={63}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.431444}, DOI={10.1063/1.431444}, number={3}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Miller, William H.}, year={1975}, month=aug, pages={1166–1172} }

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