Exchange energies with forces in density-functional theory

Abstract

We propose exchanging the energy functionals in ground-state density-functional theory with physically equivalent exact force expressions as a new promising route toward approximations to the exchange–correlation potential and energy. In analogy to the usual energy-based procedure, we split the force difference between the interacting and auxiliary Kohn–Sham system into a Hartree, an exchange, and a correlation force. The corresponding scalar potential is obtained by solving a Poisson equation, while an additional transverse part of the force yields a vector potential. These vector potentials obey an exact constraint between the exchange and correlation contribution and can further be related to the atomic shell structure. Numerically, the force-based local-exchange potential and the corresponding exchange energy compare well with the numerically more involved optimized effective potential method. Overall, the force-based method has several benefits when compared to the usual energy-based approach and opens a route toward numerically inexpensive nonlocal and (in the time-dependent case) nonadiabatic approximations.