Relativistic Two-component Double Ionization Potential Equation-of-Motion Coupled Cluster with the Dirac--Coulomb--Breit Hamiltonian
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arXiv
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| Auteurs principaux: | , , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866916864396886016 |
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| author | Li, Run R. Yuwono, Stephen H. Liebenthal, Marcus D. Zhang, Tianyuan Li, Xiaosong DePrince III, A. Eugene |
| author_facet | Li, Run R. Yuwono, Stephen H. Liebenthal, Marcus D. Zhang, Tianyuan Li, Xiaosong DePrince III, A. Eugene |
| contents | We have implemented relativistic formulations of DIP-EOMCCSD and DIP-EOMCCSDT within the 1eX2C and DC-, DCG-, and DCB-X2C frameworks. Direct comparisons against full 4c-DIP-EOMCCSD calculations show excellent agreement with DC(G)-X2C-DIP-EOMCCSD, suggesting, at least for the systems studied herein, two-electron relativistic effects are well-described by the mean-field treatment in mmfX2C, and remaining relativistic two-electron and electron-positron correlation effects are negligible. A subsequent basis set study on vertical double IPs for noble gas and diatomic species has shown that DCB-X2C-DIP-EOMCCSD tends to overestimate double IP values in the limit of a complete one-electron basis, by more than 0.25 eV, on average. For atomic systems, we were able to demonstrate that a composite scheme whereby the dominant correlation effects are captured by large-basis DCB-X2C-DIP-EOMCCSD and remaining high-order correlation effects are approximately modeled via small-basis DCB-X2C-DIP-EOMCCSDT brings the double IP values into excellent agreement with experiment; for Xe atom, for example, absolute errors in double IP values from this approach are less than 0.02 eV. However, we found the ANO-RCC family of basis sets used in our composite approach to have poor convergence behavior in terms of DCB-X2C-DIP-EOMCC calculations, as the estimates computed using the non-relativistic DIP-EOMCC approach at the large basis set limit indicates a larger 0.1--0.2 eV error relative to experimental data. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2505_00499 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Relativistic Two-component Double Ionization Potential Equation-of-Motion Coupled Cluster with the Dirac--Coulomb--Breit Hamiltonian Li, Run R. Yuwono, Stephen H. Liebenthal, Marcus D. Zhang, Tianyuan Li, Xiaosong DePrince III, A. Eugene Chemical Physics We have implemented relativistic formulations of DIP-EOMCCSD and DIP-EOMCCSDT within the 1eX2C and DC-, DCG-, and DCB-X2C frameworks. Direct comparisons against full 4c-DIP-EOMCCSD calculations show excellent agreement with DC(G)-X2C-DIP-EOMCCSD, suggesting, at least for the systems studied herein, two-electron relativistic effects are well-described by the mean-field treatment in mmfX2C, and remaining relativistic two-electron and electron-positron correlation effects are negligible. A subsequent basis set study on vertical double IPs for noble gas and diatomic species has shown that DCB-X2C-DIP-EOMCCSD tends to overestimate double IP values in the limit of a complete one-electron basis, by more than 0.25 eV, on average. For atomic systems, we were able to demonstrate that a composite scheme whereby the dominant correlation effects are captured by large-basis DCB-X2C-DIP-EOMCCSD and remaining high-order correlation effects are approximately modeled via small-basis DCB-X2C-DIP-EOMCCSDT brings the double IP values into excellent agreement with experiment; for Xe atom, for example, absolute errors in double IP values from this approach are less than 0.02 eV. However, we found the ANO-RCC family of basis sets used in our composite approach to have poor convergence behavior in terms of DCB-X2C-DIP-EOMCC calculations, as the estimates computed using the non-relativistic DIP-EOMCC approach at the large basis set limit indicates a larger 0.1--0.2 eV error relative to experimental data. |
| title | Relativistic Two-component Double Ionization Potential Equation-of-Motion Coupled Cluster with the Dirac--Coulomb--Breit Hamiltonian |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2505.00499 |