Infrared signature of structures associated with the H+(H2O)n (n=6 to 27) clusters

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 less than or equal to n less than or equal to 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.