The solvation of iodine anions in water clusters: PES studies

Markovich, Gil; Pollack, Stuart; Giniger, Rina; Cheshnovsky, Ori

doi:10.1007/bf01429115

Cited by 35 publications

(20 citation statements)

References 12 publications

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“…The analysis of this figure provides information of the size dependence on vertical ionization, a fact that has already been observed. 14,15,[23][24][25] The associated uncertainties of the E stab (n) for the larger ͓I(H 2 O) n ͔ Ϫ clusters is included in Fig. 2.…”

Section: Resultsmentioning

confidence: 99%

“…There is experimental uncertainty in the temperature of experiments which were obtained possibly around ϳ70 K. 14,15 To establish the importance of temperature effects on the cluster structure, Monte Carlo ͑MC͒ simulations of ͓X(H 2 O) n ͔ Ϫ clusters (XϵF, Br, and I͒ at 70, 150, 200, and 250 K were carried. For each cluster 200M configurations (M ϵ10 6 ) of MC simulations were produced.…”

Section: Methodsmentioning

confidence: 99%

“…PES is well established in studying the electronic structure of negatively charged clusters. [9][10][11][12][13][14][15] The aim of this work is twofold. First, the relation between cluster structure and stabilization energy, as well as the dependence of the latter with temperature are studied.…”

Section: Introductionmentioning

confidence: 99%

“…Markovich et al 14,15 present the experimental photoelectron spectra of Cl Ϫ , Br Ϫ , and I Ϫ hydrated clusters considering up to nϭ60 water molecules in the case of the iodide anion. Wang and co-workers 16 present experimental E stab up to nϭ4 for F Ϫ water clusters.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…VIE, electron affinity and detachment energy. In experiment, the vertical ionization mechanism of the hydrated halide clusters has been reported by Cheshnovsky and co-workers with the method of photoelectron spectra [10][11][12][13], and the corresponding VIEs in bulk solvent have been obtained using the extrapolation method with the experimental data from photoelectron emission spectroscopy (PEES) [14][15][16]. Direct detection of the VIE for the cations and anions in bulk solution in experiment is problematic due to their coexistences, necessitating a proper theoretical method for investigating the ionization process within the medium.…”

Section: Introductionmentioning

confidence: 90%

Vertical ionization energies of halogen anions in solution

et al. 2010

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Based on the constrained equilibrium state theory, the nonequilibrium solvation energy is derived in the framework of the continuum model. The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption. The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X  (X = Cl, Br, I, Cl 2 , Br 2 , I 2 ) in aqueous solution. According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum, our final estimated vertical ionization energies in solution are very close to the experimental observations, while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies. vertical ionization energy, spectral shift, constrained equilibrium state

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Photodetachment dynamics of closed-shell anions: Effects of perturbation by a strong neighboring dipole

Mondal

Bhattacharyya

2000

Int. J. Quantum Chem.

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The solvation of iodine anions in water clusters: PES studies

Cited by 35 publications

References 12 publications

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

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

Vertical ionization energies of halogen anions in solution

Photodetachment dynamics of closed-shell anions: Effects of perturbation by a strong neighboring dipole

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