Abstract

Investigating the dissociation of acids in the presence of a limited number of water molecules is crucial for understanding various elementary chemical processes. In our study, focusing on HCl(H 2 O) n clusters (where HCl is hydrogen chloride and H 2 O is water) formed in a cold and isolated jet expansion, we used the nuclear quadrupole coupling tensor obtained through rotational spectroscopy to decipher the nature of the hydrogen-chlorine (H-Cl) chemical bond in a microaqueous environment. For n = 1 to 4, the H-Cl bond is covalent. At n = 5 and 7, the contact ion pair of H 3 O + Cl − is spontaneously formed within the hydrogen bond networks of book and cube acid-water clusters, respectively.