Effect of the metallicity on the capacitance of gold-aqueous sodium chloride interfaces

Electrochemistry experiments have established that the capacitance of electrode-electrolyte interfaces is much larger for good metals, such as gold and platinum, than for carbon-based materials. Despite the development of elaborate electrode interaction potentials, to date molecular dynamics simulations are not able to capture this effect. Here, we show that changing the width of the Gaussian charge distribution used to represent the atomic charges in gold is an effective way to tune its metallicity. Larger Gaussian widths lead to a capacitance of aqueous solutions (pure water and 1 M NaCl) in good agreement with recent ab initio molecular dynamics results. For pure water, the increase in the capacitance is not accompanied by structural changes, while in the presence of salt, the Na+ cations tend to adsorb significantly on the surface. For a strongly metallic gold electrode, these ions can even form inner sphere complexes on hollow sites of the surface.

Automated summary

Electrochemistry experiments have shown that the capacitance of electrode-electrolyte interfaces is much larger for good metals like gold and platinum compared to carbon-based materials. By adjusting the metallicity of gold through the width of the Gaussian charge distribution, the capacitance of aqueous solutions can be modified. The presence of salt can lead to adsorption of Na+ cations on the surface of metallic gold electrodes.