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The Journal of Chemical Physics
Article . 2023 . Peer-reviewed
License: CC BY
Data sources: Crossref
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https://dx.doi.org/10.48550/ar...
Article . 2023
License: CC BY
Data sources: Datacite
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The convexity condition of density-functional theory

Authors: Andrew C. Burgess; Edward Linscott; David D. O’Regan;

The convexity condition of density-functional theory

Abstract

It has long been postulated that within density-functional theory (DFT), the total energy of a finite electronic system is convex with respect to electron count so that 2Ev[N0] ≤ Ev[N0 − 1] + Ev[N0 + 1]. Using the infinite-separation-limit technique, this Communication proves the convexity condition for any formulation of DFT that is (1) exact for all v-representable densities, (2) size-consistent, and (3) translationally invariant. An analogous result is also proven for one-body reduced density matrix functional theory. While there are known DFT formulations in which the ground state is not always accessible, indicating that convexity does not hold in such cases, this proof, nonetheless, confirms a stringent constraint on the exact exchange–correlation functional. We also provide sufficient conditions for convexity in approximate DFT, which could aid in the development of density-functional approximations. This result lifts a standing assumption in the proof of the piecewise linearity condition with respect to electron count, which has proven central to understanding the Kohn–Sham bandgap and the exchange–correlation derivative discontinuity of DFT.

Country
Ireland
Keywords

Chemical Physics (physics.chem-ph), Condensed Matter - Strongly Correlated Electrons, Quantum Physics, Strongly Correlated Electrons (cond-mat.str-el), Physics - Chemical Physics, FOS: Physical sciences, Computational Physics (physics.comp-ph), Quantum Physics (quant-ph), Physics - Computational Physics

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
13
Top 10%
Average
Top 10%
Green
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