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J Chem Phys. 2004 Jul 1;121(1):204-8.

Aqua dissociation nature of cesium hydroxide.

Author information

1
Department of Chemistry, National Creative Research Initiative Center for Superfunctional Materials, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea.

Abstract

To understand the mechanism of aqueous base dissociation chemistry, the ionic dissociation of cesium-hydroxide in water clusters is examined using density functional theory and ab initio calculations. In this study, we report hydrated structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of CsOH(H(2)O)(n=0-4). With the addition of water molecules, the Cs-OH bond lengthened significantly from 2.46 A for n=1 to 3.08 A for n=4, which causes redshift in Cs-O stretching frequency. It is found that three water molecules are needed for the dissociation of Cs-OH, in contrast to the case of strong acid dissociation which requires at least four water molecules. However, the dissociation for n=3 could be considered as incomplete because a very weak CS em leader OH stretch mode is still present, while that for n=4 is complete since the Cs em leader OH mode no longer exists. This study can be related with hydration chemistry of cations and anions, and extended into the intra- and intercharge-transfer phenomena.

PMID:
15260538
DOI:
10.1063/1.1757438

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