title: Water orientation and hydrogen-bond structure at the fluorite/water interface.
abstract: Water in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water, and are responsible for the "free OH" signature in the VSFG spectrum, which can be explained from local electronic structure effects. The quantification of the surface termination, near-surface ion distribution and water arrangement is enabled by a combination of advanced phase-resolved Vibrational Sum Frequency Generation spectra of CaF2/water interfaces and state-of-the-art ab initio molecular dynamics simulations which include electronic structure effects.
authors.affiliation: Johannes Gutenberg University Mainz, Staudingerweg 7, 55099 Mainz, Germany.
authors.forename: Rémi
authors.initials: R
authors.lastname: Khatib
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Ellen H G
authors.initials: EH
authors.lastname: Backus
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Mischa
authors.initials: M
authors.lastname: Bonn
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: María-José
authors.initials: MJ
authors.lastname: Perez-Haro
authors.affiliation: LAMBE CNRS UMR8587, Université d'Evry val d'Essonne, Boulevard F. Mitterrand, Bât Maupertuis, 91025 Evry, France.
authors.forename: Marie-Pierre
authors.initials: MP
authors.lastname: Gaigeot
authors.affiliation: Johannes Gutenberg University Mainz, Staudingerweg 7, 55099 Mainz, Germany.
authors.forename: Marialore
authors.initials: M
authors.lastname: Sulpizi