Fractional Charges, Linear Conditions and Chemical Potentials for Excited States in $ΔSCF$ Theory
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866914914695643136 |
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| author | Yang, Weitao Fan, Yichen |
| author_facet | Yang, Weitao Fan, Yichen |
| contents | To describe excited states, the electron density alone being insufficient, we use the noninteracting reference density matrix $γ_{s}({\bf x},{\bf x}')$ based on the recently established foundation for the $ΔSCF$ theory, in which ground and excited state energies and densities are obtained from the minimum and stationary solutions of the same functional. We now extend the theory to fractional charges. Based on the exact properties of degeneracy and size consistency, we show that the exact energy functional for fractional charges, expressed as a linear combination of the $γ_{s}$ of an $N-$electron and that of an $\left(N+1\right)-$electron excited state, is a straight line interpolating the energies at integers. We introduce the concepts of excited-state chemical potentials to describe the slopes of these linear lines. Numerical calculations reveal the excited-state delocalization error with common approximate functionals but good performance of corrected functionals on the proven linear conditions. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2408_08443 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Fractional Charges, Linear Conditions and Chemical Potentials for Excited States in $ΔSCF$ Theory Yang, Weitao Fan, Yichen Chemical Physics To describe excited states, the electron density alone being insufficient, we use the noninteracting reference density matrix $γ_{s}({\bf x},{\bf x}')$ based on the recently established foundation for the $ΔSCF$ theory, in which ground and excited state energies and densities are obtained from the minimum and stationary solutions of the same functional. We now extend the theory to fractional charges. Based on the exact properties of degeneracy and size consistency, we show that the exact energy functional for fractional charges, expressed as a linear combination of the $γ_{s}$ of an $N-$electron and that of an $\left(N+1\right)-$electron excited state, is a straight line interpolating the energies at integers. We introduce the concepts of excited-state chemical potentials to describe the slopes of these linear lines. Numerical calculations reveal the excited-state delocalization error with common approximate functionals but good performance of corrected functionals on the proven linear conditions. |
| title | Fractional Charges, Linear Conditions and Chemical Potentials for Excited States in $ΔSCF$ Theory |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2408.08443 |