Vibrational Spectroscopy of the Cl-(H2O)n Anionic Clusters, n = 1−5

Choi, Jong Ho; Kuwata, Keith T.; Cao, Yi Bin; Okumura, Mitchio

doi:10.1021/jp9729425

Cited by 226 publications

(200 citation statements)

References 47 publications

(44 reference statements)

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“…Also, one needs about six waters in order to distinguish between an interior and surface located ion. Therefore, we exclude from our discussion the large body of studies 4 concerning the structure of small water-halide clusters with less than six water molecules [10][11][12][13][14][15][16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Ions at the Air/Water Interface

2002

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We present results from theoretical studies of aqueous ionic solvation of alkali halides aimed at developing a microscopic description of structure and dynamics at the interface between air and salt solutions. The traditional view has depicted the air/solution interface of simple electrolytes as being devoid of ions. However, it is now firmly established that polarizable anions, such as the heavier halides, occupy the surface of small to medium sized water clusters. Using a combination of theoretical calculations, including ab initio quantum chemistry, Car-Parrinello molecular dynamics simulations, and primarily molecular dynamics simulations based on polarizable force fields, we present a unified view of the interfacial structure of aqueous ionic clusters and bulk solutions. Indeed, we demonstrate that the heavier halogen anions have a propensity for the interface that is proportional to their polarizabil- * Electronic mail: jungwirt@jh-inst.cas.cz † Electronic mail: dtobias@uci.edu 2

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Section: Introductionmentioning

confidence: 99%

Ions at the Air/Water Interface

2002

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“…These studies indicate that Cl -, Br -, and I -are asymmetrically solvated in clusters containing up to 6 water molecules. [9][10][11] The fluoride anion, on the other hand, is solvated internally in these small clusters. Larger clusters, with up to 15 water molecules, have been studied by photoelectron spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

“…8,9 Somewhat surprising, however, is the simulation result that interfacial solvation persists in clusters containing as many as 255 water molecules. 4 These results, while intriguing, have no experimental confirmation.…”

Section: Introductionmentioning

confidence: 99%

Surface Curvature Effects in the Aqueous Ionic Solvation of the Chloride Ion

1999

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Molecular dynamics simulations of hydrated chloride ions have been performed with a polarizable model for interface geometries of varying curvature, ranging from clusters to planar surfaces. The solvation depth profile of the chloride ion is found to depend dramatically on the curvature of the interface. This behavior is consistent with the structure-breaking character of the chloride ion, and is successfully analyzed in terms of a simple geometric model. This model is expected to be useful in predicting analogous behavior in other ionic species.

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“…It is interesting to consider that in the case of halide microhydration many of the optimized structures have similar energies and the order of stability can change when thermal corrections and zero point vibrational effects are included. 17,19,20,[37][38][39] Thus, it could be unsafe trying to understand the structure of ͓X(H 2 O) n ͔ Ϫ clusters in terms of local minima. In this sense, the analysis of our MC trajectories indicates how different structures with similar interaction energy present different E stab values.…”

Section: Resultsmentioning

confidence: 99%

Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

Ayala¹,

Martı́nez²,

Pappalardo³

et al. 2004

The Journal of Chemical Physics

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The aim of this work is to compute the stabilization energy E stab (n) of ͓X(H 2 O) n ͔ Ϫ (XϵF, Br, and I for nϭ1 -60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of ͓X(H 2 O) n ͔ Ϫ clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E stab (n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: ͑1͒ the Koopmans' theorem and ͑2͒ calculation of the difference between the interaction energy of ͓X(H 2 O) n ͔ Ϫ and ͓X(H 2 O) n ͔ clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E stab (n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E stab (n) and the structure of clusters has been found. The diversity of E stab (n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E stab (n) is not significant as long as it was high enough to avoid cluster trapping into local equilibrium configurations which guarantees an appropriate sampling of the configurational space. Parallel tempering method was applied in particular cases to guarantee satisfactory sampling of clusters at low temperature.

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Vibrational Spectroscopy of the Cl^-(H₂O)_n Anionic Clusters, n = 1−5

Cited by 226 publications

References 47 publications

Ions at the Air/Water Interface

Ions at the Air/Water Interface

Surface Curvature Effects in the Aqueous Ionic Solvation of the Chloride Ion

Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

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