Selection of basis sets for atoms and molecules in cavities

Abstract

A method of selection of basis functions for the quantum chemical description of atoms and molecules inside spherical and cuboidal cavities is presented. The method consists of two independent steps. First, the appropriate GTO or STO exponents are chosen by fitting the basis functions to cutoff orbitals. The criterion of maximal orbital density inside the cavity is next applied to form the final model orbital space. The method presents the fundamental advantage over many other methods of being trivially applicable in standard quantum chemical progam packages. As an illustration, the method is applied to the hydrogen atom in a spherical box. The use of contracted basis functions is also discussed. © 1996 John Wiley & Sons, Inc.