Comparison of the Monte Carlo estimation of surface electrostatic potential at the hematite (0 0 0 1)/electrolyte interface with the experiment

The Monte Carlo simulations of the surface electrostatic potential are presented for the hematite (0 0 0 1) crystal plane. According to the ab initio calculations, the Fe-terminated (0 0 0 1) plane contains only one type of surface groups. The charge of this surface group is predicted using quantum population analyses, and the result is very close to this of the 1-pK model assumption. The surface topology and topography were constructed using the relaxed crystal plane structure. The Monte Carlo simulations for the reduced (including only hydrogen ions) and the extended (containing also electrolyte) models give the linear non-Nernstian pH-profile of surface potential. The simulation results are in agreement with the experimental measurements carried out by Kallay et al. [N. Kallay, Z. Dojnović, A. Cop, J. Colloid Interface Sci. 286 (2005) 610-614.] in the point of zero charge vicinity. This suggests that in this pH-region the surface properties are basically governed by the H+ ions uptake/release and the electrolyte ions complexations. The discrepancy for strongly acidic and basic regions suggests that some additional processes take place in the single-crystal electrode measurement, which results in the non-linear ψ0=f(pH) profile.