Computing surface dipoles and potentials of self-assembled monolayers from first principles

We discuss methodological aspects of first principles calculations of surface dipoles and potentials in general, and surface-adsorbed self-assembled monolayers in particular, using density functional theory with a slab/super-cell approach. We show that calculations involving asymmetric slabs may yield highly erroneous results for the surface dipole and demonstrated the efficacy of a simple dipole correction scheme. We explain the importance of the electrostatic dipole distribution, show how to compute it, and establish conditions for the equivalence of calculations for the dipole distribution and the electrostatic potential distribution.