Aqua dissociation nature of cesium hydroxide

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.

Hydration of Barium Monohydroxide in (H2O)1–3 Clusters: Theory and Experiment

“…Owing to the neutral charge state of BaOH and the highly ionic character of its BaOH bond, it will be significant to contrast the present results with those obtained in studying the hydration process of the related MOH (M = alkaline metal) species, [14][15][16][17][18] in order to address the role of the BaOH unpaired electron on its stepwise hydration in small water clusters.…”

“…The strong Ba systems, [14][15][16][17] allow estimates in the number of water molecules which seem to be required for full dissociation of the relevant metal monohydroxides: m > 5 for BaOH, 7…”

“…In this paper we report ionization energies for BaOH( of related theoretical studies on the alkali monohydroxides, [14][15][16][17][18] which allows for an interpretation of the opposite trends that are found in the cluster size dependence of the vertical ionization energies for both series of systems, as well as addressing the similarities and differences between the corresponding stepwise hydration behaviors.…”

Communication: A concerted mechanism between proton transfer of Zundel anion and displacement of counter cation

“…[10][11][12][13] However, much less is known about what happens when H 3 O 2 − is neutralized by a counter cation. [14][15][16][17][18] This communication reports a theoretical analysis of the influence of a series of alkali metal cations M + (M = Li, Na, and K) on the structure and dynamics of the gasphase low-barrier hydrogen-bonded species M + (H 3 O 2 − ), as a first step to understand the influence of counter cations on proton transfer in basic media. First, as a conventional way, ab initio molecular orbital (MO) calculations are employed to survey the equilibrium (EQ) and the transition state (TS) structures.…”

Understanding Clusters toward the Design of Functional Molecules and Nanomaterials

“…104 Clusters of Dissociated Acids, Bases, and Salts. Investigation of aqueous clusters of acids, [111][112][113][114][115] bases, [116][117][118] and salts [119][120][121][122][123] helps us understand the dissociation phenomena of these molecules. Upon dissociation, both cations and anions are simultaneously present in the system.…”