Spectroscopic Determination of the OH − Solvation Shell in the OH − ·(H 2 O) n Clusters

Abstract

There has been long-standing uncertainty about the number of water molecules in the primary coordination environment of the OH⁻ and F⁻ ions in aqueous chemistry. We report the vibrational spectra of the OH⁻·(H₂O)_n and F⁻·(H₂O)_n clusters and interpret the pattern of OH stretching fundamentals with ab initio calculations. The spectra of the cold complexes are obtained by first attaching weakly bound argon atoms to the clusters and then monitoring the photoinduced evaporation of these atoms when an infrared laser is tuned to a vibrational resonance. The small clusters (n ≤ 3) display an isolated, sharp feature near the free OH stretching vibration, the signature of open solvation morphologies where each water molecule binds independently to the ion. Pronounced changes in the spectra are observed at n = 4 in the hydroxide ion and at n = 5 in the fluoride ion. In both cases, new features appear in the region typically associated with interwater hydrogen bonding. This behavior establishes that the primary hydration shells occur at n = 3 and 4 in hydroxide and fluoride, respectively.