A new parameterization of the DFT/CIS method with applications to core-level spectroscopy
Time-dependent density functional theory (TD-DFT) within a restricted excitation space is an efficient means to compute core-level excitation energies using only a small subset of the occupied orbitals. However, core-to-valence excitation energies are significantly underestimated when standard excha...
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Veröffentlicht in: | The Journal of chemical physics 2024-07, Vol.161 (4) |
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Sprache: | eng |
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Zusammenfassung: | Time-dependent density functional theory (TD-DFT) within a restricted excitation space is an efficient means to compute core-level excitation energies using only a small subset of the occupied orbitals. However, core-to-valence excitation energies are significantly underestimated when standard exchange–correlation functionals are used, which is partly traceable to systemic issues with TD-DFT’s description of Rydberg and charge-transfer excited states. To mitigate this, we have implemented an empirically modified combination of configuration interaction with single substitutions (CIS) based on Kohn–Sham orbitals, which is known as “DFT/CIS.” This semi-empirical approach is well-suited for simulating x-ray near-edge spectra, as it contains sufficient exact exchange to model charge-transfer excitations yet retains DFT’s low-cost description of dynamical electron correlation. Empirical corrections to the matrix elements enable semi-quantitative simulation of near-edge x-ray spectra without the need for significant a posteriori shifts; this should be useful in complex molecules and materials with multiple overlapping x-ray edges. Parameter optimization for use with a specific range-separated hybrid functional makes this a black-box method intended for both core and valence spectroscopy. Results herein demonstrate that realistic K-edge absorption and emission spectra can be obtained for second- and third-row elements and 3d transition metals, with promising results for L-edge spectra as well. DFT/CIS calculations require absolute shifts that are considerably smaller than what is typical in TD-DFT. |
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ISSN: | 0021-9606 1089-7690 1089-7690 |
DOI: | 10.1063/5.0220535 |