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An improved path-integral method for golden-rule rates

Abstract:

We present a simple method for the calculation of reaction rates in the Fermi golden-rule limit, which accurately captures the effects of tunneling and zero-point energy. The method is based on a modification of the recently proposed golden-rule quantum transition state theory (GR-QTST) of Thapa, Fang, and Richardson [J. Chem. Phys. 150, 104107 (2019)]. While GR-QTST is not size consistent, leading to the possibility of unbounded errors in the rate, our modified method has no such issue and s...

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Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1063/5.0022535

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
ORCID:
0000-0001-6546-2925
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author
ORCID:
0000-0002-7111-0763
Publisher:
American Institute of Physics Publisher's website
Journal:
Journal of Chemical Physics Journal website
Volume:
153
Issue:
15
Article number:
154113
Publication date:
2020-10-21
Acceptance date:
2020-09-11
DOI:
EISSN:
1089-7690
ISSN:
0021-9606
Pmid:
33092388
Language:
English
Keywords:
Pubs id:
1139269
Local pid:
pubs:1139269
Deposit date:
2021-03-25

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