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Register a new userSome theoretical considerations concerning ion hydration in the case of ion transfer between water and 1,2-dichloroethane
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Added by
Cristian G. Sanchez
Publication date
1997
fields
Physics
and research's language is
English
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Some aspects of direct ion transfer across the water/1,2-dichloroethane are analyzed using a very simple model based on thermodynamic considerations. It was concluded that ion solvation by water molecules may occur in some particular cases in the organic phase, delivering an important contribution to the Gibbs free energy of ion transfer between the aqueous and the organic phase. In general terms, this particular type of transfer should be favored in the case of highly charged small ions at interfaces with a relatively low surface tension and a large difference between the reciprocal of the corresponding dielectric constants.
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A series of calculations on the energetics of complexation of alkaline metals with 1,10-phenanthroline are presented. It is an experimental fact that the ordering of the free energy of transfer across the water - 1,2-dichloroethane interphase is governed by the charge / size ratio of the diferent cations; the larger cations showing the lower free energy of transfer. This ordering of the free energies of transfer is reverted in the presence of 1,10-phenanthroline in the organic phase. We have devised a thermodynamic cycle for the transfer process and by means of ab-initio calculations have drawn the conclusion that in the presence of phen the free energy of transfer is governed by the stability of the PHEN/M $^{+}$complex, which explains the observed tendency from a theoretical point of view.
Path-integral ab initio molecular dynamics (PI-AIMD) calculations have been employed to probe the nature of chloride ion solvation in aqueous solution. Nuclear quantum effects (NQEs) are shown to weaken hydrogen bonding between the chloride anion and the solvation shell of water molecules. As a consequence, the disruptive effect of the anion on the solvent water structure is significantly reduced compared to what is found in the absence of NQEs. The chloride hydration structure obtained from PI-AIMD agrees well with information extracted from neutron scattering data. Inparticular, the observed satellite peak in the hydrogen-chloride-hydrogen triple angular distribution serves as a clear signature of NQEs. The present results suggest that NQEs are likely to play acrucial role in determining the structure of saline solutions.
The stationary nonempirical simulations of Na+(H2O)n clusters with n in a range of 28 to 51 carried out at the density functional level with a hybrid B3LYP functional and the Born-Oppenheimer molecular dynamics modeling of the size selected clusters reveal the interrelated structural and energetic peculiarities of sodium hydration structures. Surface, bulk, and transient configurations of the clusters are distinguished with the different location of the sodium nucleus (close to either the spatial center of the structure or one of its side faces) and its consistently changing coordination number (which typically equals five or six). The <rNaO> mean Na-O distances for the first-shell water molecules are found to depend both on the spatial character of the structure and the local coordination of sodium. The <rNaO> values are compared to different experimental estimates, and the virtual discrepancy of the latter is explained based on the results of the cluster simulations. Different coordination neighborhoods of sodium are predicted depending on its local fraction in the actual specimens.
We carefully compare the one-dimensional WKB barrier tunneling model, and the one-channel Schodinger equation with a complex optical potential calculation of heavy-ion fusion, for a light and a heavy system. It is found that the major difference between the two approaches occurs around the critical energy, above which the effective potential for the grazing angular momentum ceases to exhibit a pocket. The value of this critical energy is shown to be strongly dependent on the nuclear potential at short distances, on the inside region of the Coulomb barrier, and this dependence is much more important for heavy systems. Therefore the nuclear fusion process is expected to provide information on the nuclear potential in this inner region. We compare calculations with available data to show that the results are consistent with this expectation.
We study the importance of self-interaction errors in density functional approximations for various water-ion clusters. We have employed the Fermi-Lowdin orbital self-interaction correction (FLOSIC) method in conjunction with LSDA, PBE, and SCAN to describe binding energies of hydrogen-bonded water-ion clusters, textit{i.e.}, water-hydronium, water-hydroxide, water-halide, as well as non-hydrogen-bonded water-alkali clusters. In the hydrogen-bonded water-ion clusters, the building blocks are linked by hydrogen atoms, although the links are much stronger and longer-ranged than the normal hydrogen bonds between water molecules, because the monopole on the ion interacts with both permanent and induced dipoles on the water molecules. We find that self-interaction errors overbind the hydrogen-bonded water-ion clusters and that FLOSIC reduces the error and brings the binding energies into closer agreement with higher-level calculations. The non-hydrogen-bonded water-alkali clusters are not significantly affected by self-interaction errors. Self-interaction corrected PBE predicts the lowest mean unsigned error in binding energies ($leq$ 50 meV/ce{H2O}) for hydrogen-bonded water-ion clusters. Self-interaction errors are also largely dependent on the cluster size, and FLOSIC does not accurately capture the subtle variation in all clusters, indicating the need for further refinement.
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