Assessment of DFT functionals for the calculation of interaction-induced electric properties of molecular complexes

A detailed evaluation of DFT methods for the calculations of the interaction-induced electric properties has been performed. H-bonded model complexes (HF center dot center dot center dot HF, H2O center dot center dot center dot H2O and H2CO center dot center dot center dot HF) have been taken for investigation. The calculations of the components of the static electric properties have been carried out employing different types of density functionals. Procured results have been compared with those obtained at the CCSD (T) level of theory. The diffuse Dunning's and Jensen's basis sets of increasing size (aug-cc-pVXZ and aug-pc-Y, respectively) have been tested. The counterpoise correction scheme has been applied in order to eliminate basis set superposition error. The present contribution shows that DFT allows to well-reproduce the CCSD (T) results for the interaction-induced dipole moment and (hyper) polarizability and PBE0 performs best of all the analyzed functionals, although no definite answer can be given of which functional is best in general. (C) 2011 Elsevier B. V. All rights reserved.