Hydration structure and free energy of biomolecularly specific aqueous dications, including Zn2+ and first transition row metals

The hydration of some of the alkaline earth divalent metal cations and first row transition metal cations is considered within the quasi-chemical theory of solutions. Quantum chemical calculations provide information on the chemically important interactions between the ion and its first-shell water molecules. A dielectric continuum model supplies the outer-shell contribution. The theory then provides the framework to mesh these quantities together. The agreement between the calculated and experimental quantities is good. For the transition metal cations, it is seen that the ligand field contributions play an important role in the physics of hydration. Removing these bonding contributions from the computed hydration free energy results in a linear decrease in the hydration free energy along the period. It is precisely such effects that molecular mechanics force fields have not captured. The implications and extensions of this study to metal atoms in proteins are suggested.