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research article

Semiclassical analysis of the quantum instanton approximation

Vaillant, Christophe L.
•
Thapa, Manish J.
•
Vaníček, Jiří  
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October 11, 2019
The Journal of Chemical Physics

We explore the relation between the quantum and semiclassical instanton approximations for the reaction rate constant. From the quantum instanton expression, we analyze the contributions to the rate constant in terms of minimum-action paths and find that two such paths dominate the expression. For symmetric barriers, these two paths join together to describe the semiclassical instanton periodic orbit. However, for asymmetric barriers, one of the two paths takes an unphysically low energy and dominates the expression, leading to order-of-magnitude errors in the rate predictions. Nevertheless, semiclassical instanton theory remains accurate. We conclude that semiclassical instanton theory can be obtained directly from the semiclassical limit of the quantum instanton for symmetric systems. We suggest a modification of the quantum instanton approach which avoids sampling the spurious path and thus has a stronger connection to semiclassical instanton theory, giving numerically accurate predictions even for very asymmetric systems in the low temperature limit.

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Type
research article
DOI
10.1063/1.5123800
Author(s)
Vaillant, Christophe L.
Thapa, Manish J.
Vaníček, Jiří  

EPFL

Richardson, Jeremy O.
Date Issued

2019-10-11

Published in
The Journal of Chemical Physics
Volume

151

Issue

14

Article Number

144111

Subjects

reaction rates

•

semiclassical theory

•

nuclear quantum effects

•

quantum dynamics

•

Eckart barrier

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
FunderGrant Number

FNS-NCCR

MUST

Available on Infoscience
October 11, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/161962
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