The description of electrode-electrolyte interfaces is based on the concept of the formation of an electric double layer. This concept was derived from continuum theories extended by introducing point charge distributions. Based on molecular dynamics simulations, we analyze the electric double layer in an approach beyond the point charge scheme by instead assessing charge polarizations at electrochemical metal-water interfaces from first principles. We show that the atomic structure of water layers at room temperature leads to an oscillatory behavior of the averaged electrostatic potential. We address the relation between the polarization distribution at the interface and the extent of the electric double layer and subsequently derive the electrode potential from the charge polarization.

The structure of a liquid water layer on Pt(111) has been studied by ab initio molecular dynamics simulations based on periodic density functional theory calculations. First the reliability of the chosen exchange-correlation function has been validated by considering water clusters, bulk ice structures, and bulk liquid water, confirming that the dispersion corrected RPBE-D3/zero functional is a suitable choice. The simulations at room temperature yield that a water layer that is six layers thick is sufficient to yield liquid water properties in the interior of the water film. Performing a statistical average along the trajectory, a mean work function of 5.01 V is derived, giving a potential of zero charge of Pt(111) of 0.57 V vs. standard hydrogen electrode, in good agreement with experiments. Therefore we propose the RPBE-D3/zero functional as the appropriate choice for first-principles calculations addressing electrochemical aqueous electrolyte/metal electrode interfaces.

Clarifying the nature of interactions between metal electrodes and organic molecules still represent one of the challenging problems in molecular electronics that needs to be solved in order to optimize electron transport through a molecular device. For this purpose, electronic properties at metal-molecule interfaces were studied by combining experimental and theoretical methods. Applying a novel electrochemical approach, strictly two-dimensional Pd islands were prepared on top of 4-mercaptopyridine self-assembled monolayers (4MP-SAMs) which, in turn, were deposited on (111)-oriented Au single crystals. Electron spectroscopy together with density functional theory calculations revealed strong interactions between the molecules and the islands due to Pd-N bonds, resulting in a drastically reduced density of states (DOS) at the Fermi level EF for a nearly closed Pd monolayer, and even non-metallic properties for nanometre-sized islands. Similarly, a significantly reduced DOS at EF was observed for the topmost Au layer at the Au-SAM interface due to Au-S interactions, suggesting that these effects are rather general.

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The CO adsorption on ordered Cu-Pd alloy surfaces and surface alloys has been studied using density functional theory (DFT) within the framework of the generalized gradient approximation (GGA). On the surface alloys, the CO adsorption energy at the top sites decreases with increasing concentration of the more reactive metal Pd. This surprising ligand effect is caused by the effective compressive strain induced by the larger size of the Pd atoms. On the other hand, at the most favorable adsorption sites the CO binding becomes stronger with increasing Pd concentration which is caused by an ensemble effect related to the availability of higher coordinated adsorption sites. At the surfaces of the bulk alloys, the trends in the adsorption energy as a function of the Pd concentration are less clear because of the strong Pd-Cu interaction and the absence of effective strain effects.