Published in

American Institute of Physics, The Journal of Chemical Physics, 2(160), 2024

DOI: 10.1063/5.0177346

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Exchange energies with forces in density-functional theory

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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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.