Efficient periodic density functional theory calculations of charged molecules and surfaces using Coulomb kernel truncation

Density functional theory (DFT) calculations of charged molecules and surfaces are critical to applications in electrocatalysis, energy materials, and related fields of materials science. DFT implementations such as the Vienna simulation package () compute the electrostatic potential under three-dimensional (3D) periodic boundary conditions, necessitating charge neutrality. In this work, we implement 0D and 2D periodic boundary conditions to facilitate DFT calculations of charged molecules and surfaces, respectively. We implement these boundary conditions using the Coulomb kernel truncation method. Our implementation computes the potential under 0D and 2D boundary conditions by selectively subtracting unwanted long-range interactions in the potential computed under 3D boundary conditions. By combining the Coulomb kernel truncation method with a computationally efficient padding approach, we remove nonphysical potentials from vacuum in 0D and 2D systems. To illustrate the computational efficiency of our method, we perform large supercell calculations of the formation energy of a charged chlorine defect on a sodium chloride (001) surface and perform long-timescale molecular dynamics simulations on a stepped gold (211) water electrode-electrolyte interface.