Application of density functional theory /Hartree-Fock hybrid methods. Geometries and bond dissociation energies of Al+ complexes

A mixture of Hartree-Fock exchange and density functional theory exchange-correlation treatment has been applied to determine the geometry and bond dissociation energies (BDEs) of cationic Al+-X complexes (X = CH3, NH3, H2O, OH, HF, HCN, HNC, CO, CN, CH2O, CO2, N2, O2, and F2). By using the local spin density approximation and the ‘Becke-3-Lee-Young-Parr’ functionals each combined with three different basis sets (i.e. 6–31 G(d, p), 6–311 + G(d, p), and 6–311 + + G(3df, 2p)), the present findings (i) show good agreement with experimental and theoretical results of Møller-Plesset, configuration interaction and Gaussian-2 (G2) calculations on BDE and geometry, (ii) yield predictions of as yet experimentally and theoretically unknown species, (iii) recommend the combination of the B3LYP /6–311 + G(d, p) method for the geometry optimization and the B3LYP /6–311 + + G(3df, 2p)/ /BB3LYP /6–311 + G(d, p) level to yield a sufficiently accurate description of the energetics of cationic aluminum complexes within a short time, and therefore (iv) support the successful application of DFT methods towards metal-ion complexes.