Ion Effects on Terahertz Spectra of Microsolvated Clusters

Abstract

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.