Interaction of surface cations of cleaved mica with water in vapor and liquid forms

Natural minerals contain ions that become hydrated when they come into contact with water in vapor and liquid forms. Muscovite mica - a common phyllosilicate with perfect cleavage planes - is an ideal system to investigate the details of ion hydration. The cleaved mica surface is decorated by an array of K⁺ ions that can be easily exchanged with other ions or protons when immersed in an aqueous solution. Despite the vast interest in the atomic-scale hydration processes of these K⁺ ions, experimental data under controlled conditions have remained elusive. Here, atomically resolved non-contact atomic force microscopy (nc-AFM) is combined with X-ray photoelectron spectroscopy (XPS) to investigate the cation hydration upon dosing water vapor at 100 K in ultra-high vacuum (UHV). The cleaved surface is further exposed to ultra-clean liquid water at room temperature, which promotes ion mobility and partial ion-to-proton substitution. The results offer the first direct experimental views of the interaction of water with muscovite mica under UHV. The findings are in line with previous theoretical predictions.