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Published Online April 29, 2004
Science DOI: 10.1126/science.1096466

Reports

Submitted on February 5, 2004
Accepted on April 5, 2004

Infrared Signature of Structures Associated with the H+(H2O)n (n = 6 to 27) Clusters

J.-W. Shin 1, N. I. Hammer 1, E. G. Diken 1, M. A. Johnson 1*, R. S. Walters 2, T. D. Jaeger 2, M. A. Duncan 2*, R. A. Christie 3, K. D. Jordan 3*

1 Sterling Chemistry Laboratory, Yale University, P. O. Box 208107, New Haven, CT 06520, USA.
2 Department of Chemistry, University of Georgia, Athens, GA 30602, USA.
3 Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.

* To whom correspondence should be addressed.
M. A. Johnson , E-mail: mark.johnson{at}yale.edu
M. A. Duncan , E-mail: maduncan{at}uga.edu
K. D. Jordan , E-mail: jordan{at}imap.pitt.edu

We report the OH stretching vibrational spectra of size-selected H+(H2O)n clusters through the region of the pronounced "magic number" at n = 21 in the cluster distribution. Sharp features are observed in the spectra and assigned to excitation of the dangling OH groups throughout the size range 6 <= n <= 27. A multiplet of such bands appears at small cluster sizes. This pattern simplifies to a doublet at n = 11, with the doublet persisting up to n = 20, but then collapsing to a single line in the n = 21 and 22 clusters and reemerging at n = 23. This spectral simplification provides direct evidence that, for the magic number cluster, all the dangling OH groups arise from water molecules in similar binding sites.


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Science. ISSN 0036-8075 (print), 1095-9203 (online)