Bulk Boundary Condition for Surface Calculations in Density Functional Theory

We present a bulk boundary condition formalism for surface calculations in Kohn--Sham density functional theory.

The approach exploits the nearsightedness of electronic interactions in real space to restrict the calculation to a localized surface region.

Within this region, the electron density is evaluated by leveraging the decay of the density matrix, with bulk values imposed on the density and electrostatic potential in the interior, and the electrostatic potential solved subject to bulk boundary conditions.

The energy and atomic forces are computed using density-matrix-based expressions.

Through representative calculations of surface and adsorption energies, we demonstrate the accuracy and efficiency of the proposed formalism.