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Theoretical study of hydrogen abstraction reactions CH4 + R → CH3 + HR, geometrical, energetical and kinetical aspects

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Abstract

Five hydrogen abstraction reactions, CH4 + R → CH3 + HR have been studied usingab initio SCF and CI methods. R was successively chosen as H, CH3, NH2, OH and F. Geometries were fully optimized at SCF level and energies were computed at CI level for products, reactants and transition states. Quadratic hypersurfaces were fitted in the neighborhood of the most important points of the potential energy hypersurfaces and vibrational analysis were performed thereupon. Wigner's and Christov's approximations were used to obtain an idea of the importance of tunneling of H atoms through the reaction barrier, and this effect was shown to be non-negligible. Finally, rate constant calculation were carried out at different temperatures.

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Author notes

  1. José Luis Villaveces

    Present address: Seccion de Fisico-Quimica, Universidad Nacional de Colombia, Ciudad Universitaria, Edificio de Quimica, Bogota, D.E., Colombia

Authors and Affiliations

  1. Université Catholique de Louvain, Laboratoire de Chimie Quantique, Bâtiment Lavoisier, Place Louis Pasteur, 11348, Louvain-la-Neuve, Belgium

    Michel Sana, Georges Leroy & José Luis Villaveces

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  1. Michel Sana
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  2. Georges Leroy
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  3. José Luis Villaveces
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Chercheur Qualifié au Fonds National Belge de la Recherche Scientifique.

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Sana, M., Leroy, G. & Villaveces, J.L. Theoretical study of hydrogen abstraction reactions CH4 + R → CH3 + HR, geometrical, energetical and kinetical aspects. Theoret. Chim. Acta 65, 109–125 (1984). https://doi.org/10.1007/BF01064207

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