AN INTERPOLATED UNRESTRICTED HARTREE-FOCK POTENTIAL ENERGY SURFACE FOR THE OH+H-2-]H2O+H REACTION

摘要

In this paper we demonstrate, at the UHF/6-311 + + G(d,p) level of theory, the practical feasibility of using a Initio quantum chemical calculations to generate a molecular potential energy surface (PES) for the OH+H-2-->H2O + H reaction using our previously suggested interpolation and iteration schemes. The successful, and almost completely automated, merger of the PES algorithm and quantum chemical calculations involves a number of significant practical problems, the solutions of which are presented in detail. The convergence of the interpolated potential surface was monitored in terms of reaction probability and we find that the surface converges once the energy, gradient and Hessian have been calculated at approximately 350 geometries. We also find that, although the initial geometries used consisted only of points along a reaction path for the OH+H-2-->H2O + H reaction, the potential energy surface iteration process rapidly adds information about other, energetically accessible, reaction channels. (C) 1996 American Institute of Physics. [References: 54]