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Comparative study of BSSE correction methods at DFT and MP2 levels of theory
Author(s) -
Paizs Béla,
Suhai Sándor
Publication year - 1998
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(19980430)19:6<575::aid-jcc1>3.0.co;2-o
Subject(s) - counterpoise , basis set , hamiltonian (control theory) , basis (linear algebra) , computational chemistry , chemistry , hydrogen bond , binding energy , density functional theory , intermolecular force , quantum mechanics , molecule , physics , mathematics , mathematical optimization , geometry
A comparative study of intermolecular potential energy curves is performed on the complexes H 2 O(SINGLE BOND)HF, H 2 O(SINGLE BOND)H 2 O, H 2 O(SINGLE BOND)H 2 S, and H 2 S(SINGLE BOND)H 2 S using nine different basis sets at the MP2 and DFT (BLYP and B3LYP) levels of theory. The basis set superposition error is corrected by means of the counterpoise scheme and based on the “chemical Hamiltonian approach.” The counterpoise and CHA‐corrected DFT curves are generally close to each other. Using small basis sets, the B3LYP functional cannot be favored against the BLYP one because the BLYP results sometimes get closer to the MP2 values than those of B3LYP. From the results—including the available literature data—we suggest that one has to use at least polarized‐valence triple‐zeta‐quality basis sets (TZV, 6‐311G) for the investigation of hydrogen‐bonded complexes. Special attention must be paid to the physical nature of the binding. If the dispersion forces become significant DFT methods are not able to describe the interaction. Proper correction for the basis set superposition error is found to be mandatory in all cases. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 575–584, 1998