Coupling of surface chemistry and electric double layer at TiO₂ electrochemical interfaces

Surfaces of metal oxides at working conditions are usually electrified due to the acid-base chemistry. The charged interface compensated with counterions forms the so-called electric double layer. The coupling of surface chemistry and electric double layer is considered to be crucial but poorly understood because of lacking the information at the atomistic scale. Here, we used the latest development in density functional theory based finite-field molecular dynamics simulation to investigate pH-dependence of the Helmholtz capacitance at electrified rutile TiO$_2$ (110)-NaCl electrolyte interfaces. It is found that, due to competing forces from surface adsorption and from electric double layer, water molecules have a stronger structural fluctuation at high pH and this leads to a much larger capacitance. It is also seen that, interfacial proton transfers at low pH increase significantly the capacitance value. These findings elucidate the microscopic origin for the same trend observed in titration experiments.