Existence and nonexistence of HOMO-LUMO excitations in Kohn-Sham density functional theory

DOI10.1016/J.NA.2020.111973MaRDI QIDQ2201735zbMATH OpenOpenAlexFDO

Authors Gero Friesecke, Benedikt R. Graswald

Publication date 17 September 2020

Published in Nonlinear Analysis. Theory, Methods \& Applications. Series A: Theory and Methods (Search for Journal in Brave)

Full work available at URL https://arxiv.org/abs/1907.00064

zbMATH Keywords

excitationsorbitalsnonlinear eigenvalue equations

Mathematics Subject Classification ID

Quantum optics (81V80) Computational methods for problems pertaining to quantum theory (81-08) Molecular physics (81V55) Numerical solution of nonlinear eigenvalue and eigenvector problems (65H17)

Abstract: In numerical computations of response properties of electronic systems, the standard model is Kohn-Sham density functional theory (KS-DFT). Here we investigate the mathematical status of the simplest class of excitations in KS-DFT, HOMO-LUMO excitations. We show using concentration-compactness arguments that such excitations, i.e. excited states of the Kohn-Sham Hamiltonian, exist for $Z>N$, where $Z$ is the total nuclear charge and $N$ is the number of electrons. The result applies under realistic assumptions on the exchange-correlation functional, which we verify explicitly for the widely used PZ81 and PW92 functionals. By contrast, and somewhat surprisingly, we find using a method of Glaser, Martin, Grosse, and Thirring cite{glaser1976} that in case of the hydrogen and helium atoms, excited states do not exist in the neutral case $Z=N$ when the self-consistent KS ground state density is replaced by a realistic but easier to analyze approximation (in case of hydrogen, the true Schr"{o}dinger ground state density). Implications for interpreting minus the HOMO eigenvalue as an approximation to the ionization potential are indicated.

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Cited in

(3)

• Extension of Kohn–Sham theory to excited states by means of an off-diagonal density array
• Sum-rules of the response potential in the strongly-interacting limit of DFT
• New optimal control problems in density functional theory motivated by photovoltaics

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