APPLICATION OF DENSITY-FUNCTIONAL METHODS FOR THE STUDY OF HYDROGEN-BONDED SYSTEMS - THE HYDROGEN-FLUORIDE DIMER

Systematic studies of the ability of a broad family of density functional methods applied to hydrogen-bonded complexes have been carried out on the hydrogen fluoride dimer. Specifically, calculations have been performed using basis sets of triple-zeta quality with diffuse functions and multiple sets of polarization functions. Various local and nonlocal exchange-correlation functionals have been applied in order to study the structure, energetics, and vibrational properties of the hydrogen fluoride dimer. The comparison with the experimental data, and also with results coming from ab initio methods (Hartree-Fock, Moller-Plesset second order, and quadratic configuration interaction with the single and double excitations) shows good performance of nonlocal density functional methods for the description of hydrogen-bonded systems. The calculated binding energy, with nonlocal Becke exchange and Lee-Yang-Parr correlation functionals and a 6-311++G(3df,3pd) basis set, is 4.48 kcal/mol and is in good agreement with experimental value and prior calculations. © 1994 American Institute of Physics.