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research article

Kinetic isotope effect in malonaldehyde determined from path integral Monte Carlo simulations

Huang, Jing
•
Buchowiecki, Marcin  
•
Nagy, Tibor
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2014
Physical Chemistry Chemical Physics

The primary H/D kinetic isotope effect on the intramolecular proton transfer in malonaldehyde is determined from quantum instanton path integral Monte Carlo simulations on a fully dimensional and validated potential energy surface for temperatures between 250 and 1500 K. Our calculations, based on thermodynamic integration with respect to the mass of the transferring particle are significantly accelerated by the direct evaluation of the kinetic isotope effect instead of computing it as a ratio of two rate constants. At room temperature, the KIE from the present simulations is 5$\pm$4. The KIE is found to vary considerably as a function of temperature and the low-T behaviour is dominated by the fact that the free energy derivative in the reactant state increases more rapidly than at the transition state. Detailed analysis of the various contributions to the quantum rate constant together with estimates for rates from conventional transition state theory and from periodic orbit theory suggest that the KIE in malonaldehyde is dominated by zero point energy effects and that tunneling plays a minor role at room temperature

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Type
research article
DOI
10.1039/c3cp53698j
Web of Science ID

WOS:000327667500022

Author(s)
Huang, Jing
Buchowiecki, Marcin  
Nagy, Tibor
Vanicek, Jiri  
Meuwly, Markus
Date Issued

2014

Publisher

Royal Society of Chemistry

Published in
Physical Chemistry Chemical Physics
Volume

16

Issue

1

Start page

204

End page

211

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
Available on Infoscience
October 25, 2013
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/96423
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