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Assessment of Grouped-Bath Configuration Interaction for Transition-Metal Complexes by L-Edge X-ray Spectra
1Department of Chemistry, Seoul National University, Seoul 08826, South Korea.
Journal of Chemical Theory and Computation
|January 16, 2026
Summary
The grouped-bath configuration interaction (GBCI) method accurately calculates X-ray spectra for transition metals by including crucial bath-orbital relaxation. This improves charge-transfer state descriptions compared to previous methods.
Area of Science:
- Computational Chemistry
- Spectroscopy
- Materials Science
Background:
- Transition-metal complexes exhibit complex electronic structures crucial for catalysis and materials.
- Accurate theoretical modeling of X-ray absorption and scattering spectra is essential for understanding these systems.
- Existing methods like spin-flip complete-active-space (SF-CAS) have limitations in describing charge-transfer states.
Purpose of the Study:
- To evaluate the accuracy and limitations of the grouped-bath configuration interaction (GBCI) method.
- To compare GBCI-calculated L-edge X-ray absorption spectroscopy (XAS) and 2p3d resonant inelastic X-ray scattering (RIXS) spectra with SF-CAS and experimental data.
- To establish GBCI as a benchmark for electronic-structure theories of transition-metal complexes.
Main Methods:
- Calculation of L-edge XAS and 2p3d RIXS spectra using the GBCI method.
- Comparison of GBCI results with SF-CAS calculations and experimental spectra.
- Analysis of bath-orbital relaxation effects on charge-transfer states.
Main Results:
- GBCI accurately describes energies and wave functions of charge-transfer states due to bath-orbital relaxation.
- GBCI accounts for core-hole relaxation in L-edge XAS, providing uniform energy shifts.
- GBCI corrects overestimated energies and intensities in 2p3d RIXS charge-transfer bands compared to SF-CAS.
Conclusions:
- GBCI offers significant improvements over SF-CAS for calculating X-ray spectra of transition-metal complexes.
- While GBCI is accurate, further inclusion of electronic correlation is needed for complete agreement with experiments.
- The presented spectral comparisons serve as a valuable benchmark for future theoretical developments.
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