On the structure of the first hydration layer on NaCl(100): role of hydrogen bonding

The authors have investigated the structure and energetics of the first hydration layer on NaCl(100) by means of density functional calculations. They have analyzed in detail the role of the hydrogen bond between the adsorbed molecules for the determination of the most favorable structures. They have shown that, using the water dimers as basic building blocks, very stable structures can be constructed. They discuss here two important examples: (i) a model with (1x1) periodicity at 2 ML coverage, and (ii) icelike bilayers with a c(4x2) unit cell at 1.5 ML. Both structures present high adsorption energies per water molecule of approximately 570 meV, in comparison to the 350 meV adsorption energy obtained for the previously studied (1x1) structures composed of weakly interacting monomers. Based on these findings, they propose an interpretation for the experimental observations of Toennies et al. [J. Chem. Phys. 120, 11347 (2004)], who found a transition of the periodicity of the first hydration layer on NaCl(100) from (1x1) to c(4x2) upon electron irradiation. According to the model, the transition would be driven by the partial desorption of (1x1) bilayer structures corresponding to a local coverage of 2 ML and the further rearrangement of the remaining water molecules to form a quasihexagonal structure with c(4x2) periodicity at coverage close to 1.5 ML.