Semiclassical evaluation of kinetic isotope effects in 13-atomic system
نویسندگان
چکیده
منابع مشابه
Semiclassical evaluation of kinetic isotope effects in 13-atomic system.
The semiclassical instanton approach discussed by Kryvohuz [J. Chem. Phys. 134, 114103 (2011)] is applied to calculate kinetic H/D isotope effect (KIE) of intramolecular hydrogen transfer in cis-1,3-pentadiene. All 33 vibrational degrees of freedom are treated quantum mechanically with semiclassical approximation. Nuclear quantum effects such as tunneling under the barrier and zero-point energy...
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Kinetic isotope effects (KIEs) [9] are the effects on chemical reaction rates caused by isotopic substitution in the reacting system. KIEs report on bonding changes to the isotopic atom(s) when going from reactant state to transition state (TS). KIE studies are therefore of great use in solving mechanistic problems such as: (i) concerted or stepwise reaction? (ii) which is the rate limiting ste...
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A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum-instanton approximation for the rate constant and on the path-integral Metropolis-Monte Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, th...
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ژورنال
عنوان ژورنال: The Journal of Chemical Physics
سال: 2012
ISSN: 0021-9606,1089-7690
DOI: 10.1063/1.4754660