A Density Functional Theory for the Average Electron Energy
| Autor: | Stefano Racioppi, Phalgun Lolur, Per Hyldgaard, Martin Rahm |
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| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | Journal of Chemical Theory and Computation. 19:799-807 |
| ISSN: | 1549-9626 1549-9618 |
| DOI: | 10.1021/acs.jctc.2c00899 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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