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2014 ; 111
(51
): 18132-7
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Site-specific vibrational spectral signatures of water molecules in the magic
H3O+ (H2O)20 and Cs+ (H2O)20 clusters
#MMPMID25489068
Fournier JA
; Wolke CT
; Johnson CJ
; Johnson MA
; Heine N
; Gewinner S
; Schöllkopf W
; Esser TK
; Fagiani MR
; Knorke H
; Asmis KR
Proc Natl Acad Sci U S A
2014[Dec]; 111
(51
): 18132-7
PMID25489068
show ga
Theoretical models of proton hydration with tens of water molecules indicate that
the excess proton is embedded on the surface of clathrate-like cage structures
with one or two water molecules in the interior. The evidence for these
structures has been indirect, however, because the experimental spectra in the
critical H-bonding region of the OH stretching vibrations have been too diffuse
to provide band patterns that distinguish between candidate structures predicted
theoretically. Here we exploit the slow cooling afforded by cryogenic ion
trapping, along with isotopic substitution, to quench water clusters attached to
the H3O(+) and Cs(+) ions into structures that yield well-resolved vibrational
bands over the entire 215- to 3,800-cm(-1) range. The magic H3O(+)(H2O)20 cluster
yields particularly clear spectral signatures that can, with the aid of ab initio
predictions, be traced to specific classes of network sites in the predicted
pentagonal dodecahedron H-bonded cage with the hydronium ion residing on the
surface.