Evaluation of Density Functionals and Basis Sets for Carbohydrates
- 4 March 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of Chemical Theory and Computation
- Vol. 5 (4), 679-692
- https://doi.org/10.1021/ct8004479
Abstract
Correlated ab initio wave function calculations using MP2/aug-cc-pVTZ model chemistry have been performed for three test sets of gas phase saccharide conformations to provide reference values for their relative energies. The test sets consist of 15 conformers of alpha- and beta-D-allopyranose, 15 of 3,6-anhydro-4-O-methyl-D-galactitol, and four Of beta-D-glucopyranose. For each set, conformational energies varied by about 7 kcal/mol. Results obtained with the Hartree-Fock method, with pure density functional approximations (DFAs) like LSDA, PBEsol, PBE, and TPSS and with hybrid DFAs like B3PW91, B3LYP, PBEh, and M05-2X, were then compared to the reference and local MP2 relative energies. Basis sets included 6-31G*, 6-31G**, 6-31+G*, 6-31+G**, 6-311+G**, 6-311++G**, cc-pVTZ(-f), cc-pVTZ, and aug-cc-pVTZ(-f). The smallest basis set that gives good DFA relative energies is 6-31+G**, and more converged results can be obtained with 6-311+G**. The optimized geometries obtained from a smaller basis set, 6-31+G*, were useful for subsequent single point energy calculations with larger basis sets. The best agreement with MP2 was shown by M05-2X, but only when using a dense DFT grid. The popular B3LYP functional is not the best for saccharide conformational studies. The B3PW91 functional gives systematically better results, but other hybrid functionals like PBEh or TPSSh are even better. Overall, the nonempirical PBE GGA and TPSS meta-GGA functionals also performed better than B3LYP.This publication has 63 references indexed in Scilit:
- The accuracy of local MP2 methods for conformational energiesMolecular Physics, 2008
- GLYCAM06: A generalizable biomolecular force field. CarbohydratesJournal of Computational Chemistry, 2007
- Towards a quantum mechanical force field for carbohydrates: a reparametrized semi-empirical MO approachChemical Physics Letters, 2004
- Proper basis set for quantum mechanical studies of potential energy surfaces of carbohydratesJournal of Molecular Structure: THEOCHEM, 2002
- Structure, Conformation, and Dynamics of Bioactive Oligosaccharides: Theoretical Approaches and Experimental ValidationsChemical Reviews, 2000
- A comparison and chemometric analysis of several molecular mechanics force fields and parameter sets applied to carbohydratesCarbohydrate Research, 1998
- The origin of the problems with the PM3 core repulsion functionJournal of Molecular Structure: THEOCHEM, 1997
- Ab initio and density functional study of the conformational space of1C4 ?-L-fucoseJournal of Computational Chemistry, 1997
- Relative stability of alternative chair forms and hydroxymethyl conformations of β-d-glucopyranoseCarbohydrate Research, 1995
- Computer Modeling of CarbohydratesPublished by American Chemical Society (ACS) ,1990