H3 + as a five-body problem described with explicitly correlated Gaussian basis sets.

Abstract

Various explicitly correlated Gaussian (ECG) basis sets are considered for the solution of the molecular Schrödinger equation with particular attention to the simplest polyatomic system, H3 +. Shortcomings and advantages are discussed for plain ECGs, ECGs with the global vector representation, floating ECGs and their numerical projection, and ECGs with complex parameters. The discussion is accompanied with particle density plots to visualize the observations. In order to be able to use large complex ECG basis sets in molecular calculations, a numerically stable algorithm is developed, the efficiency of which is demonstrated for the lowest rotationally and vibrationally excited states of H2 and H3 +.