Importance of selecting proper basis set in quantum mechanical studies of potential energy surfaces of carbohydrates

Abstract

An extensive quantum mechanical study of a water dimer suggests that the introduction of a diffuse function into the basis set, which significantly reduces the basis set superposition error (BSSE) in the hydrogen bonding energy calculation, is the key to better calculations of the potential energy surfaces of carbohydrates. This article examines the potential energy surfaces of selected d-aldo- and d-ketohexoses (a total of 82 conformers) by quantum mechanics (QM) and molecular mechanics (MM) methods. In contrast to the results with a smaller basis set (B3LYP/6-31G** 5d), we found at the higher level calculation (B3LYP/6-311++G(2d,2p)//B3LYP/6-31G** 5d) that, in most cases, the furanose forms are less stable than the pyranose forms. These discrepancies are mainly due to the fact that intramolecular hydrogen bonding energies are overestimated in the lower level calculations. The higher level QM calculations of the potential energy surfaces of d-aldo- and d-ketohexoses now are more comparable to the MM3 results. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1593–1603, 1999