The non-relativistic large-Z expansion of the exchange energy of neutral atoms provides an important input to modern non-empirical density functional approximations. Recent works report results of fitting the terms beyond the dominant term, given by the local density approximation (LDA), leading to an anomalous Z ln Z term that cannot be predicted from naïve scaling arguments. Here, we provide much more detailed data analysis of the mostly smooth asymptotic trend describing the difference between exact and LDA exchange energy, the nature of oscillations across rows of the Periodic Table, and the behavior of the LDA contribution itself. Special emphasis is given to the successes and difficulties in reproducing the exchange energy and its asymptotics with existing density functional approximations.
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28 January 2024
Research Article|
January 22 2024
Investigations of the exchange energy of neutral atoms in the large-Z limit Available to Purchase
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Jeremy J. Redd
;
Jeremy J. Redd
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Physics, Utah Valley University
, Orem, Utah 84058, USA
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Antonio C. Cancio
;
Antonio C. Cancio
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
2
Department of Physics and Astronomy, Ball State University
, Muncie, Indiana 47306, USA
a)Author to whom correspondence should be addressed: [email protected]
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Nathan Argaman
;
Nathan Argaman
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
3
Department of Physics, Ben-Gurion University
, Beer-Sheva 84105, Israel
4
Department of Physics, Nuclear Research Center—Negev
, P.O. Box 9001, Be’er Sheva 84190, Israel
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Kieron Burke
Kieron Burke
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
5
Departments of Physics and Astronomy and of Chemistry, University of California
, Irvine, California 92697, USA
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Jeremy J. Redd
1
Antonio C. Cancio
2,a)
Nathan Argaman
3,4
Kieron Burke
5
1
Department of Physics, Utah Valley University
, Orem, Utah 84058, USA
2
Department of Physics and Astronomy, Ball State University
, Muncie, Indiana 47306, USA
3
Department of Physics, Ben-Gurion University
, Beer-Sheva 84105, Israel
4
Department of Physics, Nuclear Research Center—Negev
, P.O. Box 9001, Be’er Sheva 84190, Israel
5
Departments of Physics and Astronomy and of Chemistry, University of California
, Irvine, California 92697, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 160, 044101 (2024)
Article history
Received:
September 30 2023
Accepted:
December 17 2023
Citation
Jeremy J. Redd, Antonio C. Cancio, Nathan Argaman, Kieron Burke; Investigations of the exchange energy of neutral atoms in the large-Z limit. J. Chem. Phys. 28 January 2024; 160 (4): 044101. https://doi.org/10.1063/5.0179278
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