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research article

Instanton theory of ground-state tunneling splittings with general paths

Erakovic, Mihael
•
Vaillant, Christophe L.  
•
Cvitas, Marko T.
February 28, 2020
Journal Of Chemical Physics

We derive a multidimensional instanton theory for calculating ground-state tunneling splittings in Cartesian coordinates for general paths. It is an extension of the method by Mil'nikov and Nakamura [J. Chem. Phys. 115, 6881 (2001)] to include asymmetric paths that are necessary for calculating tunneling splitting patterns in multi-well systems, such as water clusters. The approach avoids multiple expensive matrix diagonalizations to converge the fluctuation prefactor in the ring-polymer instanton (RPI) method, and instead replaces them by an integration of a Riccati differential equation. When combined with the string method for locating instantons, we avoid the need to converge the calculation with respect to the imaginary time period of the semiclassical orbit, thereby reducing the number of convergence parameters of the optimized object to just one: the number of equally spaced system replicas used to represent the instanton path. The entirety of the numerical effort is thus concentrated in optimizing the shape of the path and evaluating hessians along the path, which is a dramatic improvement over RPI. In addition to the standard instanton approximations, we neglect the coupling of vibrational modes to external rotations. The method is tested on the model potential of malonaldehyde and on the water dimer and trimer, giving close agreement with RPI at a much-reduced cost. Published under license by AIP Publishing.

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Type
research article
DOI
10.1063/1.5145278
Web of Science ID

WOS:000519832600011

Author(s)
Erakovic, Mihael
Vaillant, Christophe L.  
Cvitas, Marko T.
Date Issued

2020-02-28

Published in
Journal Of Chemical Physics
Volume

152

Issue

8

Article Number

084111

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

potential-energy surface

•

ab-initio

•

water trimer

•

locating instantons

•

dynamics

•

malonaldehyde

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dimer

•

rearrangements

•

model

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
April 2, 2020
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/167775
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