Article

Quantum instanton evaluation of the thermal rate constants and kinetic isotope effects for SiH4+H -> SiH3+H-2 reaction in full Cartesian space

Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, People's Republic of China.
The Journal of Chemical Physics (Impact Factor: 3.12). 04/2007; 126(11):114307. DOI: 10.1063/1.2714510
Source: PubMed

ABSTRACT The quantum instanton calculations of thermal rate constants for the gas-phase reaction SiH4+H-->SiH3+H2 and its deuterated analogs are presented, using an analytical potential energy surface. The quantum instanton approximation is manipulated by full dimensionality in Cartesian coordinate path integral Monte Carlo approach, thereby taking explicitly into account the effects of the whole rotation, the vibrotational coupling, and anharmonicity of the reaction system. The rates and kinetic isotope effects obtained for the temperature range of 200-1000 K show good agreements with available experimental data, which give support to the accuracy of the underlying potential surface used. In order to investigate the sole quantum effect to the rates, the authors also derive the classical limit of the quantum instanton and find that it can be exactly expressed as the classical variation transition state theory. Comparing the quantum quantities with their classical analogs in the quantum instanton formula, the authors demonstrate that the quantum correction of the prefactor is more important than that of the activation energy at the transition state.

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