Premium
Investigations of hydrogen‐bonded systems: Local density approximation and gradient corrections
Author(s) -
Kaschner R.,
Seifert G.
Publication year - 1994
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560520421
Subject(s) - chemistry , dipole , hydrogen bond , hydrogen , intermolecular force , linear combination of atomic orbitals , interaction energy , local density approximation , charge density , dimer , water dimer , atomic physics , computational chemistry , molecular physics , density functional theory , physics , quantum mechanics , molecule , basis set , organic chemistry
The applicability of the local density approximation ( LDA ) and of corresponding gradient corrections (for the exchange and correlation energy) for the treatment of the hydrogen bond is investigated. As test systems, we consider the water dimer and the H 2 O…HX complexes (X = F, Cl, Br): Using an LCAO scheme, their equilibrium geometries and interaction energies are ćalculated and compared with experimental data and with other calculations. We obtain that the LDA gives the geometries in qualitative agreement with other data, whereas the energies are overestimated. The use of the gradient corrections ( GC ) according to Becke and Perdew leads to a significant improvement of the geometry, and especially of the interaction energies. The calculations indicate further that LDA + GC should also be able to describe weaker intermolecular interactions than the usual hydrogen bond. Finally, a short discussion of the charge distribution and the dipole moments of the H 2 O…HX complexes is performed. © 1994 John Wiley & Sons, Inc.