Hellmann-Feynman, virial, and scaling requisites for the exact universal density functionals. Shape of the correlation potential and diamagnetic susceptibility for atoms
- 1 October 1985
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review A
- Vol. 32 (4) , 2010-2021
- https://doi.org/10.1103/physreva.32.2010
Abstract
By the Hellmann-Feynman theorem, the density n(r) of many electrons in the presence of external potential v(r) obeys the relationships F r n(r)∇v(r)=0 and F r n(r)r×∇v(r)=0. By the virial theorem, the interacting kinetic and electron-electron repulsion expectation values obey 2T[n]+[n]=-F r n(r)r⋅∇[δT/δn(r)+δ/δn(r)]. The exchange energy functional [n] and potential ([n];r)≡δ/δn(r) must satisfy [n]+F r n(r)r⋅∇([n];r)=0, while the correlation energy and potential must satisfy [n]+F r n(r)r⋅∇([n];r)<0. Somewhat counterintuitively, it is not true that T[]=T[n] and []=γ[n], where (r)≡n(γr) is a scaled density with scale factor γ≠1. In fact, it is impossible to partition the exact Hohenberg-Kohn functional into a piece that scales as and a piece that scales as γ, even if complete freedom with the partitioning is allowed. Instead there are universal scaling inequalities.
Keywords
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