Multiple transition states in chemical reactions. II. The effect of angular momentum in variational studies of HO2 and HeH+2 systems

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Abstract
The original Wardlaw–Marcus method for the calculation of N(E,K,R) was applied to the HO2 and HeH+2 systems. The angular momentum averaged N(E,R) curves obtained by integrating N(E,K,R) over K using two different limits for K are performed. The results with Kmax calculated along the reaction coordinate show an excellent agreement with the results from the direct calculation of N(E,R). The integration over K was also performed using the minimum of Kmax(K‡) value along the reaction coordinate, which is consistent with the fact that the system with higher K value cannot react due to the centrifugal barrier. This method produced considerably low N(E,R) curves at extremely large and small R values. However, all three results were in good agreement in the transition state region. The individual N(E,K,R) curves support the behavior of the N(E,R) curves. It was pointed out that the shape of the high‐K N(E,K,R) curves plays an important role in the final transition states of N(E,R). From these results, it was suggested that the modified method is more adequate to the bimolecular association reactions than the unimolecular decomposition reactions.

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