Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory

Abstract

The addition of diffuse functions to a double-ζ basis set is shown to be more important than increasing to a triple-ζ basis when calculating reaction energies, reaction barrier heights, and conformational energies with density functional theory, in particular with the modified Perdew−Wang density functional. It is shown that diffuse basis functions are vital to describe the relative energies between reactants, products, and transition states in isogyric reactions, and they provide enormous improvement in accuracy for conformational equilibria, using 1, 2-ethanediol and butadiene as examples. As a byproduct of the present study, we present a one-parameter hybrid density functional method optimized for sugars and sugar-like molecules; this is called MPW1S.