Carbonate and carbonate anion radicals in aqueous solutions exist as CO3(H2O)62− and CO3(H2O)6˙− respectively: the crucial role of the inner hydration sphere of anions in explaining their properties

An effort to reproduce the physical properties of CO32− and CO3˙− in water proves that one has to include an inner hydration sphere of six water molecules for both anions.

Optical Absorption Characteristics For 7F0'→5L6' and 7F0'→ 7F6' Transitions of Trivalent Americium Ion in Aqueous Electrolyte Mixtures

Optical absorption features for [Formula: see text] and [Formula: see text] transitions of trivalent americium ion were investigated in a wide range of aqueous combinations of perchloric and nitric acids (0.1–6.0 mol L−1). The developed qualitative matrix of extinction coefficients measures the cumulative impact of increasing electrolyte content, changes in the hydration zones of americium ion, and inner-sphere perturbation by nitrate on the absorbance. The effects of growing complexity of aqueous electrolyte medium were highlighted for the [Formula: see text] transition. Spectroscopy indicates the perturbation of the inner hydration sphere of trivalent f-element by one nitrate ligand.

Structure and hydrogen bonding of the hydrated selenite and selenate ions in aqueous solution

The selenite ion has an asymmetric hydration sphere with loosely electrostatically bound water molecules outside the free electron pair.

Oxygen and Hydrogen Isotopic Preference in Hydration Spheres of Magnesium and Calcium Ions

Molecular orbital calculations were performed to estimate the 18O/16O and D/H isotopic reduced partition function ratios (rpfrs) of water molecules around magnesium and calcium ions. As model for water molecules in the ith hydration sphere of the cation in aqueous solutions containing that cation, we considered water molecules in the ith hydration sphere that were surrounded by water molecules in the (i+1)th hydration sphere in clusters, M2+(H2O)n (M = Mg or Ca; n up to 100). The calculations indicated that the decreasing order of the 18O preference over 16O in the primary hydration sphere is Mg2+ > Ca2+ > bulk water. That is, water molecules in the primary hydration spheres of the Mg2+ and Ca2+ ions are expected to be enriched in the heavier isotope of oxygen relative to water molecules in bulk, and the degree of the enrichment is larger for the Mg2+ ion than for the Ca2+ ion. No such preference was observed for hydrogen isotopes in any hydration sphere or for oxygen isotopes in the secondary and outer hydration spheres.

18O/16O and D/H Isotopic Preference in Hydration Spheres of Alkali Metal Ions

With the final goal set at theoretical elucidation of experimentally observed isotope salt effects, molecular orbital calculations were performed to estimate the 18O/16O and D/H isotopic reduced partition function ratios (RPFRs) of water molecules around lithium, sodium, and potassium ions. As model water molecules in the ith hydration sphere of the cation in aqueous solutions containing that cation, we considered water molecules in the ith hydration sphere that were surrounded by water molecules in the (i+1)th hydration sphere in clusters, M+(H2O)n (M = Li, Na or K; n up to 100). The calculations indicated that the decreasing order of the 18 O preference over 16 O in the primary hydration sphere is: Li+ > (bulk water) ≥ Na+ > K+. That is, water molecules in the primary hydration spheres of the Li+, Na+, and K+ ions are, respectively, enriched, slightly depleted, and depleted in the heavier isotope of oxygen relative to water molecules in bulk. No such preference was observed for hydrogen isotopes in any hydration sphere or for oxygen isotopes in the secondary and outer hydration spheres.

D/H and 18O/16O Isotopic Reduced Partition Function Ratios ofWater Molecules around a Sodium Ion

With the final goal set at theoretical elucidation of experimentally observed isotope salt effects, molecular orbital calculations were performed to estimate the D/H and 18O/16O isotopic reduced partition function ratios (RPFRs) of water molecules around a sodium ion. As model water molecules in the ith hydration sphere of the sodium ion in sodium ion-bearing aqueous solution, we considered water molecules in the ith hydration sphere that were surrounded by water molecules in the (i+1)th hydration sphere in clusters, Na+(H2O)n (n up to 100). The calculations indicated that the 18O/16O RPFR in the primary hydration sphere is slightly smaller than that of bulk water while the D/H RPFR is practically the same as that of bulk water, and that the influence of the existence of the sodium ion is limited to the primary hydration sphere.