The difference between molecules and materials: Reassessing the role of exact conditions in density functional theory

The difference between molecules and materials: Reassessing the role of exact conditions in density functional theory

Exact conditions have long been used to guide the construction of density functional approximations. However, hundreds of empirical-based approximations tailored for chemistry are in use, of which many neglect these conditions in their design. We analyze well-known conditions and revive several obsc...

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Veröffentlicht in:The Journal of chemical physics 2023-12, Vol.159 (21)
Hauptverfasser: Pederson, Ryan, Burke, Kieron
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Sprache:eng
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Approximation
Density functional theory
Empirical analysis
Physics
Search algorithms
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container_title The Journal of chemical physics
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creator Pederson, Ryan
Burke, Kieron
description Exact conditions have long been used to guide the construction of density functional approximations. However, hundreds of empirical-based approximations tailored for chemistry are in use, of which many neglect these conditions in their design. We analyze well-known conditions and revive several obscure ones. Two crucial distinctions are drawn: that between necessary and sufficient conditions and that between all electronic densities and the subset of realistic Coulombic ground states. Simple search algorithms find that many empirical approximations satisfy many exact conditions for realistic densities and non-empirical approximations satisfy even more conditions than those enforced in their construction. The role of exact conditions in developing approximations is revisited.
doi_str_mv 10.1063/5.0172058
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subjects Approximation
Density functional theory
Empirical analysis
Physics
Search algorithms
title The difference between molecules and materials: Reassessing the role of exact conditions in density functional theory
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