Ichieda, Nobuyuki Kasuno, Megumi Banu, Khaleda Kihara, Sorin Nakamatsu, Hirohide Evaluation of Hydration Enthalpies of Monatomic Cations by Considering Both Long-Range and Short-Range Interactions The standard hydration enthalpy, Δ<i>H</i>°<sub>hyd</sub>, of a monatomic cation was calculated as the sum of (1) the enthalpy due to the long-range interaction between a hydrated ion and bulk water, Δ<i>H</i>°<sub>LR</sub>, (2) the enthalpy due to the short-range interaction between the ion and water molecules in the first hydration shell, Δ<i>H</i>°<sub>SR</sub>, and (3) the enthalpy due to the ligand field stabilization of an ion, Δ<i>H</i>°<sub>LF</sub>, which arises for a transition-metal ion. Δ<i>H</i>°<sub>LR</sub> was estimated on the basis of the Born theory assuming the radius of the hydrated ion as the interatomic distance between the ion and the oxygen atom of a water molecule in the first hydration shell,<i> r</i><sub>M</sub><sub>-</sub><sub>O</sub>, determined experimentally. Δ<i>H</i>°<sub>SR</sub> was evaluated on the basis of the donor−acceptor interaction between an ion and a water molecule coordinating to the ion, which was evaluated by the molecular orbital calculation of a monohydrated cluster of an ion combined with the Mulliken population analysis. Δ<i>H</i>°<sub>LF</sub> was calculated on the basis of the crystal field theory. Hydration enthalpies of 48 monatomic cations thus calculated agreed well with those observed experimentally. Mulliken population analysis;LF;water molecule;crystal field theory;LR;hydration shell;48 monatomic cations;ligand field stabilization;SR;enthalpy 2003-08-29
    https://acs.figshare.com/articles/journal_contribution/Evaluation_of_Hydration_Enthalpies_of_Monatomic_Cations_by_Considering_Both_Long-Range_and_Short-Range_Interactions/3725253
10.1021/jp0348171.s001