Solvated ions, structure shell

Solvated ions have a complicated structure. The solvent molecules nearest to the ion form the primary, or nearest, solvation sheath (Fig. 7.2). Owing to the small distances, ion-dipole interaction in this sheath is strong and the sheath is stable. It is unaffected by thermal motion of the ion or solvent molecules, and when an ion moves it carries along its entire primary shell. In the secondary, or farther shells, interactions are weaker one notices an orientation of the solvent molecules under the effect of the ion. The disturbance among the solvent molecules caused by the ions becomes weaker with increasing distance and with increasing temperature. 

Despite the fact that the structure of the interface between a metal and an electrolyte solution has been the subject of numerous experimental and theoretical studies since the early days of physical chemistry," our understanding of this important system is still incomplete. One problem has been the unavailability (until recently) of experimental data that can provide direct structural information at the interface. For example, despite the fact that much is known about the structure of the ion s solvation shell from experimental and theoretical studies in bulk electrolyte solutions, " information about the structure of the adsorbed ion solvation shell has been mainly inferred from the measured capacity of the interface. The interface between a metal and an electrolyte solution is also very complex. One needs to consider simultaneously the electronic structure of the metal and the molecular structure of the water and the solvated ions in the inhomogeneous surface region. The availability of more direct experimental information through methods that are sensitive to the microscopic... 

The structure of the adsorbed ion coordination shell is determined by the competition between the water-ion and the metal-ion interactions, and by the constraints imposed on the water by the metal surface. This structure can be characterized by water-ion radial distribution functions and water-ion orientational probability distribution functions. Much is known about this structure from X-ray and neutron scattering measurements performed in bulk solutions, and these are generally in agreement with computer simulations. The goal of molecular dynamics simulations of ions at the metal/water interface has been to examine to what degree the structure of the ion solvation shell is modified at the interface. 

Salts, ions, and ionic liquids in water are widely studied in AIMD. Several anions [165-172], cations [153, 165, 173-182], and ion pairs [164, 183, 184], as weU as ionic hquids ion pairs [185] in water were studied using AIMD. In all cases structural as well as dynamical properties of the ion s hydration shell were examined. In some cases the influence of the solvated ions on the water molecules were studied within the Wannier approach. In general, little effect of the halogen ions on the dipole moments of the water molecules in the first hydration shell was observed, while further water molecules remain unaffected. In contrast to this, it was observed that cations increase the dipole moments of the first hydration shell water by approximately 0.2-0.5 D. The second hydration shell and the bulk phase water molecules were mostly unaffected with regard to the dipole moment by the cations as well [91]. 

The authors then develop a model for an ionic solution based on that of Frank and Wen, but in this case not restricted to the solvent water. Briefly, they consider a dynamic picture of the solvated ion which takes into account the structural differences between the three regions of solvent, which they call A, B, and C (Figure 5). Region A is the inner solvation shell of the metal ion, where the solvent molecules are held by the cation. Immediately outside this first layer is region B, where two powerful directive influences are in competition a solvent molecule may have largely... 

The statistical results for the water and ion structures shall be used to determine the electric field which is acting on the polymer chain. As the discussion above has shown the problem is much more difficult due to the missing periodicity (from nucleotide to nucleotide subunit) in the position of the ions and,therefore also in the geometrical arrangement of the solvating water molecules. A more detailed analysis of the obtained structure of the hydration shell is required, to find out wether it is possible to... 

The structure of the ions, where the bulky phenyl groups surround the central ion in a tetrahedron, lends validity to the assumption that the interaction of the shell of the ions with the environment is van der Waals in nature and identical for both ions, while the interaction of the ionic charge with the environment can be described by the Born approximation (see Section 1.2), leading to identical solvation energies for the anion and cation. 

Experiments made at higher degrees of aggregation have provided strong evidence192 for ring-like structures for mixed neutral clusters. For example, under a wide variety of experimental conditions, mixed cluster ions display a maximum intensity atm = 2(n + 1) whenn<5 for (NH3)II (M)mH+, andm = n + 2 whenn<4 for (H20)B(M)mH+ M is a proton acceptor such as acetone, pyridine, and trimethy-lamine. These findings reveal that the cluster ions with these compositions have stable solvation shell structures as discussed above. 

The effect of the ion on the strength of the hydrogen bond between water molecules dies off rapidly in the outer shells of the clusters. Almost the same values are observed in the third solvation layer and in tetrahedral water clusters. Chain structures discussed by Burton and Daly 220> show an analogous behavior (Table 19). 

Note Added in Proof After we sent the manuscript to the publishers we became aware of CNDO studies on alkali ion solvation performed by Gupta and Rao 270> and Balasubramanian et al.271 >, which might be of some importance for readers interested in cation solvation by water and various amides. Another CNDO model investigation on the structure of hydrated ions was published very recently by Cremaschi and Simonetta 272> They studied CH5 and CH5 surrounded by a first shell of water molecules in order to discuss solvation effects on structure and stability of these organic intermediates or transition states respectively. 

Although the potential energy functions can be made to reproduce thermodynamic solvation data quite well, they are not without problems. In some cases, the structure of the ion solvation shell, and in particular the coordination number, deviates from experimental data. The marked sensitivity of calculated thermodynamic data for ion pairs on the potential parameters is also a problem. Attempts to alleviate these problems by introducing polarizable ion-water potentials (which take into account the induced dipole on the water caused by the ion strong electric field) have been made, and this is still an active area of research. 

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