Water clusters containing Na+ and Cl- ions play a key role in the atmospheric chemistry of sea salt aerosols. While Na+ is clearly buried deep inside, Cl- appears to be a chameleon since evidence for both surface-localized and interior solvation states are reported. Thus, disclosing the preferred location of Cl- within clusters remains challenging. Here, we investigate whether THz spectroscopy, a powerful tool for directly probing hydrogen bonds in water, provides insights into the location of Cl- ions in water clusters. We performed ab initio molecular dynamics simulations on water clusters containing a single Cl- ion and up to 64 water molecules to compute the THz spectra with reference to Na+ and bulk. The THz spectrum of the 64-water Cl- cluster closely agrees with that of the bulk solution. Surprisingly, this match is not caused by bulk-like solvation of Cl- as suggested by phenomenological line shape analyses. Instead, the similarity stems from Cl- being mostly located at the cluster surface, thus leaving the water-water interactions largely unperturbed.
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