American Chemical Society
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Quantized Hydration Energies of Ions and Structure of Hydration Shell from the Experimental Gas-Phase Data

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journal contribution
posted on 2008-05-01, 00:00 authored by Jiří Rais, Tatsuhiro Okada
With previous data on alkali metal and halide ions included [Rais, J.; Okada, T. Anal. Sci. 2006, 22, 533], we analyzed rather broad data on ionic hydration from the point of view of gaseous cluster energetics. We have now added alkaline earth cations, Zn2+, H+, OH-, Cu+, Ag+, Bi+, Pb+, and alkylammonium cations. The present analysis revealed the octa-coordinated nature of alkaline earth cations, which is not fully pronounced for Be2+ and Zn2+, existence of Eigen protonium complex, which is trigonally hydrated, and particular property of the first OH-, H2O cluster. Whereas these findings are generally in accordance with theoretical model calculation studies, we have foreseen in addition tetrahedral hydration for halide anions and Rb+ and Cs+, as well as for alkylammonium ions. The obtained picture of the quantized solvation of ions is mirrored in the ionization potentials of outer electrons of pertinent atoms. This is a second independent phenomenon, and together, they invoked a common pattern formation (“Aufbau”) obeying tetra- and octa-coordinated principles.