Theoretical Studies of Proton-Transfer Reactions. II. The Reaction of Water with Hydride Ion

The results of computation of the potential energy surface for the reaction of water with hydride ion are described. The LCAO-MO-SCF method, using Gaussian basis functions, with all integrals analytically evaluated has been used, and the final calculations are believed to be quite close to the Hartree-Fock limits. The computations show the absence of a classical activation barrier for the reaction. The theoretical results are compared with experimental data which have been reported in the literature, and it is found not only that the results are consistent, but that the theoretical results provide an explanation of otherwise puzzling isotope effects on the solution reaction. Attention is called to the role of solvent in providing activation energies for proton-transfer reactions in solution.