Path integral representation of the reaction rate constant in quantum mechanical transition state theory
نویسندگان
چکیده
منابع مشابه
Generalized path integral based quantum transition state theory
A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H from a 2 Ž . Cu 110 surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a ‘reaction coordinate’ in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature,...
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Thermal rate constants are calculated for the H + CH(4) --> CH(3) + H(2) reaction employing the potential energy surface of Espinosa-Garcia (Espinosa-Garcia, J. J. Chem. Phys. 2002, 116, 10664). Two theoretical approaches are used. First, we employ the multiconfigurational time-dependent Hartree method combined with flux correlation functions. In this way rate constants in the range 225-400 K a...
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For proton transfer reactions, the tunneling contributions to the rates are often much larger than thermally activated rates at temperatures of interest. A number of separable tunneling corrections have been proposed that capture the dependence of tunneling rates on barrier height and imaginary frequency size. However, the effects of reaction pathway curvature and barrier anharmonicity are more...
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The quantum instanton approximation for thermal rate constants, a type of quantum transition state theory (QTST), is applied to a model proton transfer reaction in liquid methyl chloride developed by Azzouz and Borgis. Monte Carlo path integral methods are used to carry out the calculations, and two other closely related QTST's, namely, the centroid-density and Hansen-Andersen QTST, are also ev...
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The quantum state of a wormhole can be represented by a path integral over all asymptotically Euclidean four-geometries and all matter fields which have prescribed values, the arguments of the wave function, on a three-surface S which divides the spacetime manifold into two disconnected parts. The ground-state wave function is picked out by requiring that there be no matter excitations in the a...
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ژورنال
عنوان ژورنال: The Journal of Chemical Physics
سال: 1975
ISSN: 0021-9606,1089-7690
DOI: 10.1063/1.431444