| Autor: |
Janesko BG; Department of Chemistry & Biochemistry, Texas Christian University, Fort Worth, Texas 76129, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of chemical theory and computation [J Chem Theory Comput] 2023 Aug 08; Vol. 19 (15), pp. 5112-5121. Date of Electronic Publication: 2023 Jul 12. |
| DOI: |
10.1021/acs.jctc.3c00312 |
| Abstrakt: |
Linear response time-dependent density functional theory (TDDFT) is widely applied to valence, Rydberg, and charge-transfer excitations but, in its current form, makes large errors for core-electron excitations. This work demonstrates that the admixture of nonlocal exact exchange in atomic core regions significantly improves TDDFT-predicted core excitations. Exact exchange admixture is accomplished using projected hybrid density functional theory [ J. Chem. Theory Comput. 2023, 19, 837-847]. Scalar relativistic TDDFT calculations using core-projected B3LYP accurately model core excitations of second-period elements C-F and third-period elements Si-Cl, without sacrificing performance for the relative shifts of core excitation energies. Predicted K-edge X-ray near absorption edge structure (XANES) of a series of sulfur standards highlight the value of this approach. Core-projected hybrids appear to be a practical solution to TDDFT's limitations for core excitations, in the way that long-range-corrected hybrids are a practical solution to TDDFT's limitations for Rydberg and charge-transfer excitations. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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