DOI: 10.1063/1.467965. Photoelectron spectroscopy of Cl−, Br−, and I− solvated in water clusters

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

10.1063/1.467965

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We present the photoelectron-spectra of Cl−, Br−, and I−, solvated in water clusters-(H2O)n, where n is 1–7, 1–16, and 1–60, respectively, taken with 7.1 eV photon energy. The vertical binding energies of the solvated anions are used to extract the solvent electrostatic stabilization energies of the anion. The photoelectron spectra of the solvated I− indicate the formation of the first solvation layer with a coordination number of six. Ab initio calculations support solvation shell closure at n=6. This conclusion is not born-out by current molecular dynamics calculations. These calculations favor structures with a surface solvated anion (coordination number of 3–4) and reproduce (within 0.2 eV) our vertical binding energies. The fitting of the experimental binding energies of large I−(H2O)n to the models of classical electrostatic solvation is consistent with surface solvation. In the size range n=34–40 we have detected special cluster structures, with very low electrostatic stabilization.

Bibliography

Markovich, G., Pollack, S., Giniger, R., & Cheshnovsky, O. (1994). Photoelectron spectroscopy of Clâ, Brâ, and Iâ solvated in water clusters. The Journal of Chemical Physics, 101(11), 9344â9353.

Authors 4

Gil Markovich (first)
Stuart Pollack (additional)
Rina Giniger (additional)
Ori Cheshnovsky (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:12 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 7:01 p.m.)
Indexed	1 hour, 5 minutes ago (Sept. 3, 2025, 12:03 a.m.)
Issued	30 years, 9 months ago (Dec. 1, 1994)
Published	30 years, 9 months ago (Dec. 1, 1994)
Published Print	30 years, 9 months ago (Dec. 1, 1994)

Funders 0

None

BibTeX

@article{Markovich_1994, title={Photoelectron spectroscopy of Cl−, Br−, and I− solvated in water clusters}, volume={101}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.467965}, DOI={10.1063/1.467965}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Markovich, Gil and Pollack, Stuart and Giniger, Rina and Cheshnovsky, Ori}, year={1994}, month=dec, pages={9344–9353} }

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  "abstract": "<jats:p>We present the photoelectron-spectra of Cl\u2212, Br\u2212, and I\u2212, solvated in water clusters-(H2O)n, where n is 1\u20137, 1\u201316, and 1\u201360, respectively, taken with 7.1 eV photon energy. The vertical binding energies of the solvated anions are used to extract the solvent electrostatic stabilization energies of the anion. The photoelectron spectra of the solvated I\u2212 indicate the formation of the first solvation layer with a coordination number of six. Ab\u2008initio calculations support solvation shell closure at n=6. This conclusion is not born-out by current molecular dynamics calculations. These calculations favor structures with a surface solvated anion (coordination number of 3\u20134) and reproduce (within 0.2 eV) our vertical binding energies. The fitting of the experimental binding energies of large I\u2212(H2O)n to the models of classical electrostatic solvation is consistent with surface solvation. In the size range n=34\u201340 we have detected special cluster structures, with very low electrostatic stabilization.</jats:p>",
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