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Kinetic study on the H + SiH4 abstraction reaction using an ab initio potential energy surface.

Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
The Journal of Chemical Physics (Impact Factor: 3.12). 01/2011; 134(2):024315. DOI: 10.1063/1.3521477
Source: PubMed

ABSTRACT Variational transition state theory calculations with the correction of multidimensional tunneling are performed on a 12-dimensional ab initio potential energy surface for the H + SiH(4) abstraction reaction. The surface is constructed using a dual-level strategy. For the temperature range 200-1600 K, thermal rate constants are calculated and kinetic isotope effects for various isotopic species of the title reaction are investigated. The results are in very good agreement with available experimental data.

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    ABSTRACT: Thermal rate constants and kinetic isotope effects for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The obtained results are in good agreement with experimental measurements at high temperatures. The detailed investigation reveals that the anharmonicity of the hindered internal rotation motion does not influence the rate too much compared to its harmonic oscillator approximation. However, the motion of the nonreactive methyl group in C(2)H(6) significantly enhances the rates compared to its rigid case, which makes conventional reduced-dimensionality calculations a challenge. In addition, the temperature dependence of kinetic isotope effects is also revealed.
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