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  4. Path integral evaluation of the equilibrium isotope effect in [1,5] sigmatropic hydrogen shift reactions
 
journal article

Path integral evaluation of the equilibrium isotope effect in [1,5] sigmatropic hydrogen shift reactions

Zimmermann, Tomas  
•
Vanicek, Jiri  
2009
Flash informatique

The path integral methodology for computation of the equilibrium isotope effect is described and applied to three [1,5] sigmatropic hydrogen shift reactions. An efficient estimator for the derivative of the free energy is used, which shortens the computation time by the factor of about 60. Calculations reveal that the correction beyond the usual harmonic approximation for nuclear motion amount up to 30 % of the symmetry reduced reaction free energy. The numerical results are compared with recent experiments of Doering and coworkers, confirming the accuracy of the most recent measurement as well as concerns about compromised accuracy, due to side reactions, of another measurement.

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Type
journal article
Author(s)
Zimmermann, Tomas  
Vanicek, Jiri  
Date Issued

2009

Published in
Flash informatique
Issue

8

Start page

37

End page

40

Editorial or Peer reviewed

NON-REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
April 6, 2010
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/49132
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