Journal article
Overdestabilization vs Overstabilization in the Theoretical Analysis of f-Orbital Covalency
Journal of the American Chemical Society, Vol.146(17), pp.12030-12039
05/01/2024
DOI: 10.1021/jacs.4c01665
PMID: 38648269
Abstract
The complex nature of the f-orbital electronic structures and their interaction with the chemical environment pose significant computational challenges. Advanced computational techniques that variationally include scalar relativities and spin-orbit coupling directly at the molecular orbital level have been developed to address this complexity. Among these, variational relativistic multiconfigurational multireference methods stand out for their high accuracy and systematic improvement in studies of f-block complexes. Additionally, these advanced methods offer the potential for calibrating low-scaling electronic structure methods such as density functional theory. However, studies on the Cl K-edge X-ray absorption spectra of the [Ce(III)Cl
]
and [Ce(IV)Cl
]
complexes show that time-dependent density functional theory with approximate exchange-correlation kernels can lead to inaccuracies, resulting in an overstabilization of 4f orbitals and incorrect assessments of covalency. In contrast, approaches utilizing small active space wave function methods may understate the stability of these orbitals. The results herein demonstrate the need for large active space, multireference, and variational relativistic methods in studying f-block complexes.
Details
- Title: Subtitle
- Overdestabilization vs Overstabilization in the Theoretical Analysis of f-Orbital Covalency
- Creators
- Kirill D Shumilov - University of WashingtonAndrew J Jenkins - University of WashingtonHenry S La Pierre - Pacific Northwest National LaboratoryBess Vlaisavljevich - University of South DakotaXiaosong Li - University of Washington
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.146(17), pp.12030-12039
- DOI
- 10.1021/jacs.4c01665
- PMID
- 38648269
- eISSN
- 1520-5126
- Language
- English
- Electronic publication date
- 04/22/2024
- Date published
- 05/01/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984618634302771
Metrics
7 Record Views