Atomic Ionization: sd energy imbalance and Perdew-Zunger self-interaction correction energy penalty in 3d atoms
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arXiv
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| Format: | Preprint |
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2024
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| author | Maniar, Rohan Shukla, Priyanka B. Johnson, J. Karl Jackson, Koblar A. Perdew, John P. |
| author_facet | Maniar, Rohan Shukla, Priyanka B. Johnson, J. Karl Jackson, Koblar A. Perdew, John P. |
| contents | To accurately describe the energetics of transition metal systems, density functional approximations (DFAs) must provide a balanced description of s- and d- electrons. One measure of this is the sd transfer error, which has previously been defined as $E(\mathrm{3d}^{n-1}\mathrm{4s}^{1}) - E(\mathrm{3d}^{n-2}\mathrm{4s}^{2})$. Theoretical concerns have been raised about this definition due to its evaluation of excited-state energies using ground-state DFAs. A more serious concern appears to be strong correlation in the ${4s}^2$ configuration. Here we define a ground-state measure of the sd energy imbalance, based on the errors of s- and d-electron second ionization energies of the 3d atoms, that effectively circumvents the aforementioned problems. We find an improved performance as we move from LSDA to PBE to r$^2$SCAN for first-row transition metal atoms. However, we find large (~ 2 eV) ground-state sd energy imbalances when applying a Perdew-Zunger 1981 self-interaction correction. This is attributed to an "energy penalty" associated with the noded 3d orbitals. A local scaling of the self-interaction correction to LSDA results in a balance of s- and d-errors. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2409_07438 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Atomic Ionization: sd energy imbalance and Perdew-Zunger self-interaction correction energy penalty in 3d atoms Maniar, Rohan Shukla, Priyanka B. Johnson, J. Karl Jackson, Koblar A. Perdew, John P. Chemical Physics To accurately describe the energetics of transition metal systems, density functional approximations (DFAs) must provide a balanced description of s- and d- electrons. One measure of this is the sd transfer error, which has previously been defined as $E(\mathrm{3d}^{n-1}\mathrm{4s}^{1}) - E(\mathrm{3d}^{n-2}\mathrm{4s}^{2})$. Theoretical concerns have been raised about this definition due to its evaluation of excited-state energies using ground-state DFAs. A more serious concern appears to be strong correlation in the ${4s}^2$ configuration. Here we define a ground-state measure of the sd energy imbalance, based on the errors of s- and d-electron second ionization energies of the 3d atoms, that effectively circumvents the aforementioned problems. We find an improved performance as we move from LSDA to PBE to r$^2$SCAN for first-row transition metal atoms. However, we find large (~ 2 eV) ground-state sd energy imbalances when applying a Perdew-Zunger 1981 self-interaction correction. This is attributed to an "energy penalty" associated with the noded 3d orbitals. A local scaling of the self-interaction correction to LSDA results in a balance of s- and d-errors. |
| title | Atomic Ionization: sd energy imbalance and Perdew-Zunger self-interaction correction energy penalty in 3d atoms |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2409.07438 |