Precise Kohn-Sham total-energy calculations at reduced cost (1811.06788v1)

Abstract: The standard way to calculate the Kohn-Sham orbitals utilizes an approximation of the potential. The approximation consists in a projection of the potential into a finite subspace of basis functions. The orbitals, calculated with the projected potential, are used to evaluate the kinetic part of the total energy, but the true potential is used to evaluate the interaction energy with the electron density. Consequently, the Kohn-Sham total-energy expression loses its stationary behaviour as a functional of the potential. It will be discussed that this stationarity is important for the calculation of precise total energies at low computational cost and an approach will be presented that practically restores stationarity by perturbation theory. The advantage of this approach will be illustrated with total-energy results for the example of a disordered CrFeCoNi high entropy alloy.