Abstract
The reaction path hamiltonian is used to investigate the isomerisation CH3O → CH2OH; the reaction path, the frequencies along it and the coupling coefficients describing reaction path curvature were calculated by ab-initio methods. Correlation effects were included by configuration interaction using a double-zeta-plus-polarisation basis set. Including both tunnelling and curvature gives temperature dependent rate constants in broad agreement with experiment, whereas previous results were in error by several orders of magnitude.
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Colwell, S.M. Tunnelling and reaction path curvature effects in the isomerization of the methoxy radical. Theoret. Chim. Acta 74, 123–135 (1988). https://doi.org/10.1007/BF00528322
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DOI: https://doi.org/10.1007/BF00528322