Correlated ab initio quantum chemical calculations of di‐ and trisaccharide conformations

High level correlated quantum chemical calculations, using MP2 and local MP2 theory, have been performed for conformations of the disaccharide, β‐maltose, and the trisaccharide, 3,6‐di‐O‐(α‐D‐mannopyranosyl)‐α‐D‐mannopyranose. For β‐maltose, MP2 and local MP2 calculations using the 6‐311++G** basis set are in good agreement, predicting a global minimum gas‐phase conformation with a counterclockwise hydrogen bond network and the experimentally‐observed intersaccharide hydrogen bonding arrangement. For conformations of 3,6‐di‐O‐(α‐D‐mannopyranosyl)‐α‐D‐mannopyranose, MP2/6‐311++G**, and local MP2/6‐311++G** calculations do not provide a consensus prediction of relative energetics, with the MP2 method finding large differences in stability between extended and folded trisaccharide conformations. Local MP2 calculations, less susceptible to intramolecular basis set superposition errors, predict a narrower range of trisaccharide energetics, in line with estimates from Hartree–Fock theory and B3LYP and BP86 density functionals. All levels of theory predict compact, highly hydrogen‐bonded conformations as lowest in energy on the in vacuo potential energy surface of the trisaccharide. These high level, correlated local MP2/6‐311++G** calculations of di‐ and trisaccharide energetics constitute potential reference data in the development and testing of improved empirical and semiempirical potentials for modeling of carbohydrates in the condensed phase. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007