Automatic generation of potential energy and property surfaces of polyatomic molecules in normal coordinates

Abstract

A procedure for the automatic construction of Born-Oppenheimer (BO) potential energy and molecular property surfaces in rectilinear normal coordinates is presented and its suitability and accuracy when combined with vibrational structure calculations are assessed. The procedure relies on a hierarchical n-mode representation of the BO potential energy or molecular property surface, where the n-mode term of the sequence of potentials/molecular properties includes only the couplings between n or less vibrational degrees of freedom. Each n-mode cut of the energy/molecular property surface is first evaluated in a grid of points with ab initio electronic structure methods. The ab initio data are then spline interpolated and a subsequent polynomial fitting provides an analytical semiglobal representation for use in vibrational structure programs. The implementation of the procedure is outlined and the accuracy of the method is tested on water and difluoromethane. Strategies for improving the proposed algorithm are also discussed.