On the Position of the Highest Occupied Molecular Orbital in Aqueous Solutions of Simple Ions



The energies of the highest occupied molecular orbital (HOMO) of four simple microsolvated aqua ion clusters (Na+, Ag+, Cl, CN) are computed for varying numbers of water molecules. Extrapolating to infinite hydration numbers we find that these energies approach a value of −6 eV. This limiting one-electron energy is within a margin of ±1 eV independent of the character of the ion and is 4 eV lower compared to the estimate obtained for the HOMO energy of the ions in aqueous solution under periodic boundary conditions. We argue that this discrepancy must the attributed to a shift in the reference of the one-electron potential of the periodic solvent model.