Premium
A comparison of the behavior of functional/basis set combinations for hydrogen‐bonding in the water dimer with emphasis on basis set superposition error
Author(s) -
Plumley Joshua A.,
Dannenberg J. J.
Publication year - 2011
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/jcc.21729
Subject(s) - counterpoise , basis set , basis (linear algebra) , density functional theory , water dimer , sto ng basis sets , hybrid functional , set (abstract data type) , dimer , computational chemistry , basis function , chemistry , statistical physics , mathematics , hydrogen bond , computer science , molecule , physics , quantum mechanics , geometry , organic chemistry , linear combination of atomic orbitals , programming language
We evaluate the performance of ten functionals (B3LYP, M05, M05‐2X, M06, M06‐2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6‐31G(d) to aug‐cc‐pV5Z for the calculation of the H‐bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H‐bonded systems. We have compared the results to the best non‐density functional theory (non‐DFT) molecular orbital (MO) calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise (CP) corrected PES. The calculated interaction energies (Δ E s) with the largest basis sets vary from −4.42 (B97D) to −5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, because of error compensation, the smaller basis sets gave the best results (in comparison to experimental and high‐level non‐DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. As many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: (1) D95(d,p) with B3LYP, B97D, M06, or MPWB1k; (2) 6‐311G(d,p) with B3LYP; (3) D95++(d,p) with B3LYP, B97D, or MPWB1K; (4) 6‐311++G(d,p) with B3LYP or B97D; and (5) aug‐cc‐pVDZ with M05‐2X, M06‐2X, or X3LYP. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011