Generalized path integral based quantum transition state theory

G. Mills; G. K. Schenter; D. E. Makarov; H. Jónsson

doi:10.1016/S0009-2614(97)00886-5

Generalized path integral based quantum transition state theory

G. Mills
, G. K. Schenter
, D. E. Makarov
, H. Jónsson

Faculty of Physical Sciences

University of Iceland

Research output: Contribution to journal › Article › peer-review

Abstract

A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H₂ from a Cu(110) surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a 'reaction coordinate' in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature, harmonic limit the theory reduces to instanton theory. Above the cross-over temperature for tunneling, the theory reduces to the centroid density approximation and in the classical limit, variational classical transition state theory is recovered.

Original language	English
Pages (from-to)	91-96
Number of pages	6
Journal	Chemical Physics Letters
Volume	278
Issue number	1-3
DOIs	https://doi.org/10.1016/S0009-2614(97)00886-5
Publication status	Published - 24 Oct 1997

Bibliographical note

Funding Information: supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy under grant No. DE-FG06-91ER 14224 (GM and HJ) and under Contract No. DE-AC06-76RLO 1830 with Battelle Memorial Institute which operates the Pacific Northwest National Laboratory (GS and DM). GM is a Hertz foundation graduate fellow.

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title = "Generalized path integral based quantum transition state theory",

abstract = "A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H2 from a Cu(110) surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a 'reaction coordinate' in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature, harmonic limit the theory reduces to instanton theory. Above the cross-over temperature for tunneling, the theory reduces to the centroid density approximation and in the classical limit, variational classical transition state theory is recovered.",

author = "G. Mills and Schenter, \{G. K.\} and Makarov, \{D. E.\} and H. J{\'o}nsson",

note = "Funding Information: supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy under grant No. DE-FG06-91ER 14224 (GM and HJ) and under Contract No. DE-AC06-76RLO 1830 with Battelle Memorial Institute which operates the Pacific Northwest National Laboratory (GS and DM). GM is a Hertz foundation graduate fellow.",

year = "1997",

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doi = "10.1016/S0009-2614(97)00886-5",

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T1 - Generalized path integral based quantum transition state theory

AU - Mills, G.

AU - Schenter, G. K.

AU - Makarov, D. E.

AU - Jónsson, H.

N1 - Funding Information: supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy under grant No. DE-FG06-91ER 14224 (GM and HJ) and under Contract No. DE-AC06-76RLO 1830 with Battelle Memorial Institute which operates the Pacific Northwest National Laboratory (GS and DM). GM is a Hertz foundation graduate fellow.

PY - 1997/10/24

Y1 - 1997/10/24

N2 - A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H2 from a Cu(110) surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a 'reaction coordinate' in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature, harmonic limit the theory reduces to instanton theory. Above the cross-over temperature for tunneling, the theory reduces to the centroid density approximation and in the classical limit, variational classical transition state theory is recovered.

AB - A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H2 from a Cu(110) surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a 'reaction coordinate' in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature, harmonic limit the theory reduces to instanton theory. Above the cross-over temperature for tunneling, the theory reduces to the centroid density approximation and in the classical limit, variational classical transition state theory is recovered.

UR - https://www.scopus.com/pages/publications/0031585449

U2 - 10.1016/S0009-2614(97)00886-5

DO - 10.1016/S0009-2614(97)00886-5

M3 - Article

SN - 0009-2614

VL - 278

SP - 91

EP - 96

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-3

ER -

Generalized path integral based quantum transition state theory

Abstract

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