10.1021/jp0348171.s001
Nobuyuki Ichieda
Nobuyuki
Ichieda
Megumi Kasuno
Megumi
Kasuno
Khaleda Banu
Khaleda
Banu
Sorin Kihara
Sorin
Kihara
Hirohide Nakamatsu
Hirohide
Nakamatsu
Evaluation of Hydration Enthalpies of Monatomic Cations by Considering Both
Long-Range and Short-Range Interactions
American Chemical Society
2003
Mulliken population analysis
LF
water molecule
crystal field theory
LR
hydration shell
48 monatomic cations
ligand field stabilization
SR
enthalpy
2003-08-29 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Evaluation_of_Hydration_Enthalpies_of_Monatomic_Cations_by_Considering_Both_Long-Range_and_Short-Range_Interactions/3725253
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.