Comprehensive Study on the Solvation of Mono- and Divalent Metal Cations: Li+, Na+, K+, Be2+, Mg2+ and Ca2+

Abstract

Hydration of mono- and divalent metal ions (Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺ and Ca²⁺) has been studied using the DFT (B3LYP), second-order Møller−Plesset (MP2) and CCSD(T) perturbation theory as well as the G3 quantum chemical methods. Double-ζ and triple-ζ basis sets containing both (multiple) polarization and diffuse functions were applied. Total and sequential binding energies are evaluated for all metal−water clusters containing 1−6 water molecules. Total binding energies predicted at lower levels of theory are compared with those from the high level G3 calculations, whereas the sequential binding energies are compared with available experimental values. An increase in the quality of the basis set from double-ζ to triple-ζ has a significant effect on the sequential binding energies, irrespective of the geometries used. Within the same group (I or II), the sequential binding energy predictions at the MP2 and B3LYP vary appreciably. We noticed that, for each addition of a water molecule, the change of the M-O distance in metal−water clusters is higher at the B3LYP than at the MP2 level. The charge of the metal ion decreases monotonically as the number of water molecules increase in the complex.