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Perdew JP, Ruzsinszky A, Constantin LA, et al. Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed. J Chem Theory Comput. 2009;5(4):902-8doi: 10.1021/ct800531s.
Perdew, J. P., Ruzsinszky, A., Constantin, L. A., Sun, J., & Csonka, G. I. (2009). Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed. Journal of chemical theory and computation, 5(4), 902-8. https://doi.org/10.1021/ct800531s
Perdew, John P, et al. "Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed." Journal of chemical theory and computation vol. 5,4 (2009): 902-8. doi: https://doi.org/10.1021/ct800531s
Perdew JP, Ruzsinszky A, Constantin LA, Sun J, Csonka GI. Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed. J Chem Theory Comput. 2009 Apr 14;5(4):902-8. doi: 10.1021/ct800531s. Epub 2009 Mar 02. PMID: 26609599.
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J Chem Theory Comput. 2009 Apr 14;5(4):902-8. doi: 10.1021/ct800531s. Epub 2009 Mar 02.

Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed.

Journal of chemical theory and computation

John P Perdew, Adrienn Ruzsinszky, Lucian A Constantin, Jianwei Sun, Gábor I Csonka

Affiliations

  1. Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, and Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary.

PMID: 26609599 DOI: 10.1021/ct800531s

Abstract

Some fundamental issues in ground-state density functional theory are discussed without equations: (1) The standard Hohenberg-Kohn and Kohn-Sham theorems were proven for a Hamiltonian that is not quite exact for real atoms, molecules, and solids. (2) The density functional for the exchange-correlation energy, which must be approximated, arises from the tendency of electrons to avoid one another as they move through the electron density. (3) In the absence of a magnetic field, either spin densities or total electron density can be used, although the former choice is better for approximations. (4) "Spin contamination" of the determinant of Kohn-Sham orbitals for an open-shell system is not wrong but right. (5) Only to the extent that symmetries of the interacting wave function are reflected in the spin densities should those symmetries be respected by the Kohn-Sham noninteracting or determinantal wave function. Functionals below the highest level of approximations should however sometimes break even those symmetries, for good physical reasons. (6) Simple and commonly used semilocal (lower-level) approximations for the exchange-correlation energy as a functional of the density can be accurate for closed systems near equilibrium and yet fail for open systems of fluctuating electron number. (7) The exact Kohn-Sham noninteracting state need not be a single determinant, but common approximations can fail when it is not. (8) Over an open system of fluctuating electron number, connected to another such system by stretched bonds, semilocal approximations make the exchange-correlation energy and hole-density sum rule too negative. (9) The gap in the exact Kohn-Sham band structure of a crystal underestimates the real fundamental gap but may approximate the first exciton energy in the large-gap limit. (10) Density functional theory is not really a mean-field theory, although it looks like one. The exact functional includes strong correlation, and semilocal approximations often overestimate the strength of static correlation through their semilocal exchange contributions. (11) Only under rare conditions can excited states arise directly from a ground-state theory.

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