Mechanistic insights into rubidium ion adsorption at the quartz (101) surface from quantum chemical metadynamics

Abstract

Ion sorption extent and mechanism depend in part on the mineral surface termination, which can be highly complex. Variations in surface functional groups, particularly with defect density and surface roughness, influence mineral reactivity towards solutes. In this work, we investigate the adsorption of a rubidium cation (Rb⁺) at pristine and defect quartz (101) surface sites using well-tempered metadynamics, based on simulations with the quantum chemical density-functional tight-binding (DFTB) method. We compare the relative energetics of Rb⁺ adsorption across selected sites for each surface, with nanosecond-level sampling, highlighting similarities between vicinal and geminal silanol sites. We find that the positive Rb⁺ partial atomic charge can increase by as much as 0.5e as it approaches the surface, with implications for modulation of ion adsorption strength and extent at the quartz (101) surface with surface vacancies, silanol coverage, and charge.