Algebraic Diagrammatic Construction Theory of Charged Excitations With Consistent Treatment of Spin-Orbit Coupling and Dynamic Correlation
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| Format: | Preprint |
| Publié: |
2024
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| _version_ | 1866915278882865152 |
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| author | Majumder, Rajat Sokolov, Alexander Yu. |
| author_facet | Majumder, Rajat Sokolov, Alexander Yu. |
| contents | We present algebraic diagrammatic construction theory for simulating spin-orbit coupling and electron correlation in charged electronic states and photoelectron spectra. Our implementation supports Hartree-Fock and multiconfigurational reference wavefunctions, enabling efficient correlated calculations of relativistic effects using single-reference (SR-) and multireference (MR-) ADC. We combine the SR- and MR-ADC methods with three flavors of spin-orbit two-component Hamiltonians and benchmark their performance for a variety of atoms and small molecules. When multireference effects are not important, the SR-ADC approximations are competitive in accuracy to MR-ADC, often showing closer agreement with experimental results. However, for electronic states with multiconfigurational character and in non-equilibrium regions of potential energy surfaces, the MR-ADC methods are more reliable, predicting accurate excitation energies and zero-field splittings. Our results demonstrate that the spin-orbit ADC methods are promising approaches for interpreting and predicting the results of modern spectroscopies. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2412_18542 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Algebraic Diagrammatic Construction Theory of Charged Excitations With Consistent Treatment of Spin-Orbit Coupling and Dynamic Correlation Majumder, Rajat Sokolov, Alexander Yu. Chemical Physics We present algebraic diagrammatic construction theory for simulating spin-orbit coupling and electron correlation in charged electronic states and photoelectron spectra. Our implementation supports Hartree-Fock and multiconfigurational reference wavefunctions, enabling efficient correlated calculations of relativistic effects using single-reference (SR-) and multireference (MR-) ADC. We combine the SR- and MR-ADC methods with three flavors of spin-orbit two-component Hamiltonians and benchmark their performance for a variety of atoms and small molecules. When multireference effects are not important, the SR-ADC approximations are competitive in accuracy to MR-ADC, often showing closer agreement with experimental results. However, for electronic states with multiconfigurational character and in non-equilibrium regions of potential energy surfaces, the MR-ADC methods are more reliable, predicting accurate excitation energies and zero-field splittings. Our results demonstrate that the spin-orbit ADC methods are promising approaches for interpreting and predicting the results of modern spectroscopies. |
| title | Algebraic Diagrammatic Construction Theory of Charged Excitations With Consistent Treatment of Spin-Orbit Coupling and Dynamic Correlation |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2412.18542 |