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Investigating metal-ion solvation-in particular, the fundamental binding interactions-enhances the understanding of many processes, including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn 2  + (H 2 O)  n  ; n = 1-20) were measured in the O-H stretching region, using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes, calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory, the spectra show that water molecules preferentially bind to one Zn atom, adopting water binding motifs similar to the Zn + (H 2 O)  n  complexes studied previously. A lower coordination number of 2 was observed for Zn 2  + (H 2 O) 3 , evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3, attributed to a particularly low calculated Zn binding energy for this cluster size.

Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)