title: On the Reliability of Pure and Hybrid DFT Methods for the Evaluation of Halogen, Chalcogen, and Pnicogen Bonds Involving Anionic and Neutral Electron Donors.
abstract: In this article, we report a comprehensive theoretical study of halogen, chalcogen, and pnicogen bonding interactions using a large set of pure and hybrid functionals and some ab initio methods. We have observed that the pure and some hybrid functionals largely overestimate the interaction energies when the donor atom is anionic (Cl(-) or Br(-)), especially in the halogen bonding complexes. To evaluate the reliability of the different DFT (BP86, BP86-D3, BLYP, BLYP-D3, B3LYP, B97-D, B97-D3, PBE0, HSE06, APFD, and M06-2X) and ab initio (MP2, RI-MP2, and HF) methods, we have compared the binding energies and equilibrium distances to those obtained using the CCSD(T)/aug-cc-pVTZ level of theory, as reference. The addition of the latest available correction for dispersion (D3) to pure functionals is not recommended for the calculation of halogen, chalcogen, and pnicogen complexes with anions, since it further contributes to the overestimation of the binding energies. In addition, in chalcogen bonding interactions, we have studied how the hybridization of the chalcogen atom influences the interaction energies.
authors.affiliation: Departament de Química, Universitat de les Illes Balears , Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), Spain.
authors.forename: Antonio
authors.initials: A
authors.lastname: Bauzá
authors.affiliation: Instituto de Química Médica (IQM-CSIC) , Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.affiliation: Departament de Química, Universitat de les Illes Balears , Crta. de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), Spain.
authors.forename: Antonio
authors.initials: A
authors.lastname: Frontera
authors.affiliation: Instituto de Química Médica (IQM-CSIC) , Juan de la Cierva 3, 28006 Madrid, Spain.
authors.forename: José
authors.initials: J
authors.lastname: Elguero