DOI: 10.1126/science.1080695. Spectroscopic Determination of the OH − Solvation Shell in the OH − ·(H 2 O) n Clusters

Spectroscopic Determination of the OH − Solvation Shell in the OH − ·(H 2 O) n Clusters

10.1126/science.1080695

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

There has been long-standing uncertainty about the number of water molecules in the primary coordination environment of the OH − and F − ions in aqueous chemistry. We report the vibrational spectra of the OH − ·(H 2 O) n and F − ·(H 2 O) n clusters and interpret the pattern of OH stretching fundamentals with ab initio calculations. The spectra of the cold complexes are obtained by first attaching weakly bound argon atoms to the clusters and then monitoring the photoinduced evaporation of these atoms when an infrared laser is tuned to a vibrational resonance. The small clusters ( n ≤ 3) display an isolated, sharp feature near the free OH stretching vibration, the signature of open solvation morphologies where each water molecule binds independently to the ion. Pronounced changes in the spectra are observed at n = 4 in the hydroxide ion and at n = 5 in the fluoride ion. In both cases, new features appear in the region typically associated with interwater hydrogen bonding. This behavior establishes that the primary hydration shells occur at n = 3 and 4 in hydroxide and fluoride, respectively.

Bibliography

Robertson, W. H., Diken, E. G., Price, E. A., Shin, J.-W., & Johnson, M. A. (2003). Spectroscopic Determination of the OH â Solvation Shell in the OH â Â·(H 2 O) n Clusters. Science, 299(5611), 1367â1372.

Authors 5

William H. Robertson (first)
Eric G. Diken (additional)
Erica A. Price (additional)
Joong-Won Shin (additional)
Mark A. Johnson (additional)

References 51 Referenced 372

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We thank the National Science Foundation Experimental Physical Chemistry Division and the U.S. Department of Energy under grant DE-FG02-00ER15066 for support of this work. We also thank G. H. Weddle for his early work that led to the formation of hydroxide ions associated with argon atoms in the ion source.

Dates

Type	When
Created	22 years, 6 months ago (Feb. 27, 2003, 6:26 p.m.)
Deposited	1 year, 7 months ago (Jan. 9, 2024, 9:15 p.m.)
Indexed	2 days ago (Aug. 27, 2025, 12:25 p.m.)
Issued	22 years, 6 months ago (Feb. 28, 2003)
Published	22 years, 6 months ago (Feb. 28, 2003)
Published Print	22 years, 6 months ago (Feb. 28, 2003)

Funders 0

None

BibTeX

@article{Robertson_2003, title={Spectroscopic Determination of the OH − Solvation Shell in the OH − ·(H 2 O) n Clusters}, volume={299}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1080695}, DOI={10.1126/science.1080695}, number={5611}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Robertson, William H. and Diken, Eric G. and Price, Erica A. and Shin, Joong-Won and Johnson, Mark A.}, year={2003}, month=feb, pages={1367–1372} }

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