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Originally published in Science Express on 29 April 2004
Science 21 May 2004:
Vol. 304. no. 5674, pp. 1137 - 1140
DOI: 10.1126/science.1096466
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Reports

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. Jordan3*

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 n = 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.

1 Sterling Chemistry Laboratory, Yale University, Post Office 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. E-mail: mark.johnson{at}yale.edu (M.A.J.); maduncan{at}uga.edu (M.A.D.); jordan{at}imap.pitt.edu (K.D.J.)

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