Relativistic Core-Valence-Separated Molecular Mean-Field Exact-Two-Component Equation-of-Motion Coupled Cluster Theory: Applications to L-edge X-ray Absorption Spectroscopy
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| Main Authors: | , , , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866912725733474304 |
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| author | Banerjee, Samragni Li, Run R. Cooper, Brandon C. Zhang, Tianyuan Valeev, Edward F. Li, Xiaosong DePrince III, A. Eugene |
| author_facet | Banerjee, Samragni Li, Run R. Cooper, Brandon C. Zhang, Tianyuan Valeev, Edward F. Li, Xiaosong DePrince III, A. Eugene |
| contents | L-edge X-ray absorption spectra for first-row transition metal complexes are obtained from relativistic equation-of-motion singles and doubles coupled-cluster (EOM-CCSD) calculations that make use of the core-valence separation (CVS) scheme, with scalar and spin--orbit relativistic effects modeled within the molecular mean-field exact two-component (X2C) framework. By incorporating relativistic effects variationally at the Dirac--Coulomb--Breit (DCB) reference level, this method delivers accurate predictions of L-edge features, including energy shifts, intensity ratios, and fine-structure splittings, across a range of molecular systems. Benchmarking against perturbative spin--orbit treatments and relativistic TDDFT highlights the superior performance and robustness of the CVS-DCB-X2C-EOM-CCSD approach, including the reliability of basis set recontraction schemes. While limitations remain in describing high-density spectral regions, our results establish CVS-DCB-X2C-EOM-CCSD as a powerful and broadly applicable tool for relativistic core-excitation spectroscopy. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2506_09008 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Relativistic Core-Valence-Separated Molecular Mean-Field Exact-Two-Component Equation-of-Motion Coupled Cluster Theory: Applications to L-edge X-ray Absorption Spectroscopy Banerjee, Samragni Li, Run R. Cooper, Brandon C. Zhang, Tianyuan Valeev, Edward F. Li, Xiaosong DePrince III, A. Eugene Chemical Physics L-edge X-ray absorption spectra for first-row transition metal complexes are obtained from relativistic equation-of-motion singles and doubles coupled-cluster (EOM-CCSD) calculations that make use of the core-valence separation (CVS) scheme, with scalar and spin--orbit relativistic effects modeled within the molecular mean-field exact two-component (X2C) framework. By incorporating relativistic effects variationally at the Dirac--Coulomb--Breit (DCB) reference level, this method delivers accurate predictions of L-edge features, including energy shifts, intensity ratios, and fine-structure splittings, across a range of molecular systems. Benchmarking against perturbative spin--orbit treatments and relativistic TDDFT highlights the superior performance and robustness of the CVS-DCB-X2C-EOM-CCSD approach, including the reliability of basis set recontraction schemes. While limitations remain in describing high-density spectral regions, our results establish CVS-DCB-X2C-EOM-CCSD as a powerful and broadly applicable tool for relativistic core-excitation spectroscopy. |
| title | Relativistic Core-Valence-Separated Molecular Mean-Field Exact-Two-Component Equation-of-Motion Coupled Cluster Theory: Applications to L-edge X-ray Absorption Spectroscopy |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.09008 |