Theoretical and Computational Chemistry

A Density Functional Theory for the Average Electron Energy



A formally exact density functional theory (DFT) determination of the average electron energy is presented. Our theory, which is based on a different accounting of energy functional terms, partially solves one well known downside of conventional Kohn-Sham (KS) DFT: that electronic energies have but tenuous connections to physical quantities. Calculated average electron energies are close to experimental ionization potentials in one-electron systems, demonstrating a surprisingly small effect of self-interaction and other exchange-correlation errors in established DFT methods. Remarkable agreement with ab initio quantum mechanical calculations of multi-electron systems is demonstrated using several flavors of DFT, and we argue for the use of the average electron energy as a design criterion for density functional approximations.

Version notes

This version is more clearly distinguished from past work by added literature citations. The focus is now solely on the average electron energy and the part on constraining KS energy levels has been removed.


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Supplementary material

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Supporting Information for "A Density Functional Theory for the Average Electron Energy"
Materials and Methods, Supplementary Text and References, Tables S1 to S3.