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research article

Monte Carlo evaluation of the equilibrium isotope effects using the Takahashi-Imada factorization of the Feynman path integral

Buchowiecki, Marcin  
•
Vanicek, Jiri  
2013
Chemical Physics Letters

The Feynman path integral approach for computing equilibrium isotope effects and isotope fractionation corrects the approximations made in standard methods, although at significantly increased computational cost. We describe an accelerated path integral approach based on three ingredients: the fourth- order Takahashi-Imada factorization of the path integral, thermodynamic integration with respect to mass, and centroid virial estimators for relevant free energy derivatives. While the frst ingredient speeds up convergence to the quantum limit, the second and third improve statistical convergence. The combined method is applied to compute the equilibrium constants for isotope exchange reactions H2+D=H+HD and H2+D2=2HD.

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Type
research article
DOI
10.1016/j.cplett.2013.09.070
Web of Science ID

WOS:000326870500002

Author(s)
Buchowiecki, Marcin  
Vanicek, Jiri  
Date Issued

2013

Publisher

Elsevier

Published in
Chemical Physics Letters
Volume

588

Start page

11

End page

16

Note

in press.

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
October 9, 2013
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/96159
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