Exploring Expansions of the Potential and Dipole Surfaces Used for Vibrational Perturbation Theory.

Abstract

A scheme for evaluating expansions of the potential and dipole moment surfaces for vibrational perturbation theory is described. The approach is based on numerical differentiation of the Hessian in the coordinates of interest. It is shown that performing these calculations in internal coordinates generates expansions that are transferable among isotopologues of the molecule of interest. Additionally, re-expressing the expansion of the potential in terms of functions of the internal coordinates, for example, cosines of angles or exponential functions of the bond length displacements, provides expansions that can be used for higher-order perturbation theory calculations. The approach is explored and the results are discussed for water, HOD, ammonia, isomers of HNO3, and halogenated methane.