The corrections to rate constants for an harmonicity of vibrational excited states have been evaluated over the temperature range of 200–1100 K. The reaction O2 + X, where X is H or D, has been chosen as the model system. Only the influence of vibrational anharmonicity of the triatomic transition state has been determined. Two geometric shapes for the transition state, bent and isosceles configurations, have been investigated in detail by the bond order method.It is found that the correction can be large, depending upon the geometry and force field of the transition state and the temperature. The magnitude of the correction for anharmonicity of the vibrational excited states depends mainly, at a particular temperature, on the strength of the O—X bond in the transition state. In the case of a large correction, anharmonicity may lead to a nonlinear Arrhenius plot.Because of cancellation effects, the correction for anharmonicity of the excited vibrational states in kinetic isotope effects can be ignored in the lower temperature region. It has also been found that anharmonicity of the vibrational groundstate can explain unexpected large isotope effects.
