Photoelectron spectroscopy of Cl−, Br−, and I− solvated in water clusters

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

doi:10.1063/1.467965

Cited by 323 publications

(296 citation statements)

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“…NO 3 -(H 2 O) 5 . The experimental IRMPD spectrum of NO 3 -(H 2 O) 5 (see Figure 6) reveals three peaks at 1327, 1368, and 1667 cm -1 .…”

Section: Ivd Nomentioning

confidence: 99%

“…Spectroscopic experiments on isolated anion-water clusters can aid in characterizing the solvent-solute (and solvent-solvent) interaction at the molecular level one water molecule at a time. 5,6 In this work we investigate the microhydration of NO 3 -through the infrared spectroscopy of NO 3 -(H 2 O) n clusters, n ) 1-6. The gas-phase vibrational spectroscopy of NO 3 -· Ar was studied recently by Johnson and co-workers.…”

Section: Introductionmentioning

confidence: 99%

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Infrared Spectroscopy of the Microhydrated Nitrate Ions NO₃⁻(H₂O)₁₋₆

et al. 2009

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We present infrared photodissociation spectra of the microhydrated nitrate ions NO 3 -(H 2 O) 1-6 , measured from 600 to 1800 cm -1 . The assignment of the spectra is aided by comparison with calculated B3LYP/augcc-pVDZ harmonic frequencies, as well as with higher-level calculations. The IR spectra are dominated by the antisymmetric stretching mode of NO 3 -, which is doubly degenerate in the bare ion but splits into its two components for most microhydrated ions studied here due to asymmetric solvation of the nitrate core. However, for NO 3 -(H 2 O) 3 , the spectrum reveals no lifting of this degeneracy, indicating an ion with a highly symmetric solvation shell. The first three water molecules bind in a bidentate fashion to the terminal oxygen atoms of the nitrate ion, keeping the planar symmetry. The onset of extensive water-water hydrogen bonding is observed starting with four water molecules and persists in the larger clusters.

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“…NO 3 -(H 2 O) 5 . The experimental IRMPD spectrum of NO 3 -(H 2 O) 5 (see Figure 6) reveals three peaks at 1327, 1368, and 1667 cm -1 .…”

Section: Ivd Nomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Infrared Spectroscopy of the Microhydrated Nitrate Ions NO₃⁻(H₂O)₁₋₆

et al. 2009

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“…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%

“…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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