Performance of molecular orbital methods and density functional theory in the computation of geometries and energies of metal aqua ions.
Geometries and energies of various metal aqua ions have been computed with Hartree-Fock (HF), single-reference second-order perturbation theory according to Møller and Plesset (MP2), complete active space self-consistent field (CAS-SCF) methods, multi-configurational quasi-degenerate second-order perturbation theory (MCQDPT2), and density functional theory (DFT), whereby for the latter the most widely used functionals BLYP, B3LYP, LDA ("local density approximation"), and another functional (SOP) exhibiting Slater exchange, have been investigated. The geometries as well as the energies are sensitive to the computational method, results of which can lead to different conclusions. The geometries of certain reactants, products, intermediates, or transition states cannot be obtained with all of the above-mentioned computational methods: in some cases, the structures are very poor, exhibiting large errors in the bond parameters, and in others, the targeted species cannot be calculated at all. The different computational techniques do not always predict the same coordination number of a given aqua ion or the same preferred water exchange mechanism. Inaccuracies arising from inadequate basis sets are also discussed.
Rotzinger
François P
FP
Ecole Polytechnique Fédérale, Institut des Sciences et Ingénierie Chimiques, Station 6, CH-1015 Lausanne, Switzerland. francois.rotzinger@epfl.ch