Efficient global representations of potential energy functions: trajectory calculations of bimolecular gas-phase reactions by multiconfiguration molecular mechanics

Abstract

Multiconfiguration molecular mechanics (MCMM) was previously applied to calculate potential energies, gradients, and Hessians along a reaction path and in the large-curvature tunneling swath, and it was shown that one could calculate variational transition state theory rate constants with optimized multidimensional tunneling without requiring more than a few electronic structure Hessians. It was also used for molecular dynamics simulations of liquid-phase potentials of mean force as functions of a reaction coordinate. In the present article we present some improvements to the formalism and also show that with these improvements we can use the method for the harder problem of trajectory calculations on gas-phase bimolecular reactive collisions. In particular, we apply the MCMM algorithm to the model reaction OH + H(2) --> H(2)O + H, for which we construct the global full-dimensional interpolated potential energy surfaces with various numbers of electronic structure Hessians and various molecular mechanics force fields, and we assess the quality of these fits by quasiclassical trajectory calculations. We demonstrate that chemical accuracy (1-2 kcal/mol) can be reached for a MCMM potential in dynamically important regions with a fairly small number of electronic structure Hessians. We also discuss the origins of the errors in the interpolated energies and a possible way to improve the accuracy.