Electrostatic model for treating long-range lateral interactions between polar molecules adsorbed on metal surfaces

A classical polarizable point-dipole model for the adsorption of polar molecules on metal surfaces is presented. The main usefulness of the model is that lattice sums are represented by simple functions in closed form. This allows a simple extrapolation of adsorption energies of polar molecules-as calculated by first-principles calculations employing periodic boundary conditions-to the zero-coverage limit. Such an extrapolation is rather important for the proper evaluation of adsorption energy of highly polar molecules, because their long-range lateral interactions can extend beyond the nearest-neighbor distances of 50 bohrs. Moreover, the dependence of the adsorption energy on the orientation and configuration of molecular dipoles can be straightforwardly analyzed. It is demonstrated that an accumulation of polar molecules on the surface is favored provided that the molecular dipoles point parallel to the surface in the adsorbed state, whereas adsorbed molecules displaying dipoles oriented perpendicular to the surface would prefer to stay well separated due to repulsive lateral interactions. Further, the model is used to analyze the density-functional theory (DFT) calculated data of two polar molecules, triazole and benzotriazole, adsorbed onto Cu(111) surface. The DFT-calculated adsorption energies are about -0.5 eV, and it is shown that the main contribution to the molecule-surface bonding comes from the dipole-dipole electrostatic interactions.