Investigations of the exchange energy of neutral atoms in the large-Z limit (bibtex)

by Redd, Jeremy J., Cancio, Antonio C., Argaman, Nathan and Burke, Kieron

Abstract:

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.

DOI link

Reference:

Investigations of the exchange energy of neutral atoms in the large-Z limit Redd, Jeremy J., Cancio, Antonio C., Argaman, Nathan and Burke, Kieron, The Journal of Chemical Physics 160, 044101 (2024).

Bibtex Entry:

@article{RCAB24,
    Pub-num 	   = {231},
    author = {Redd, Jeremy J. and Cancio, Antonio C. and Argaman, Nathan and Burke, Kieron},
    title = {Investigations of the exchange energy of neutral atoms in the large-Z limit},
    journal = {The Journal of Chemical Physics},
    volume = {160},
    number = {4},
    pages = {044101},
    year = {2024},
    month = {01},
    abstract = "{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.}",
    issn = {0021-9606},
    doi = {10.1063/5.0179278},
    url = {https://doi.org/10.1063/5.0179278},
    eprint = {https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0179278/18626997/044101\_1\_5.0179278.pdf},
    arXiv={2310.03982}
}