Changing the paradigm in f-containing cold molecules: the impact of spin-orbit coupling and f-d transitions on quasi-bound vibrational states
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arXiv
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| Format: | Preprint |
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2024
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| author | Gałyńska, Marta de Moraes, Matheus M. F. Tecmer, Paweł Boguslawski, Katharina |
| author_facet | Gałyńska, Marta de Moraes, Matheus M. F. Tecmer, Paweł Boguslawski, Katharina |
| contents | Present-day state-of-the-art ab initio many-body calculations on f-block containing cold molecules heavily focus on perturbative approaches for spin-orbit coupling and exclude a substantial part of the atomic transitions in the $f$- and $d$-shell. Here, we demonstrate the cruciality of a proper relativistic treatment of the $f$- and $d$-shell in Yb-containing diatomics and the inclusion of $f\rightarrow d$ transitions to obtain physically sound elastic scatterings and pre-dissociation lifetimes. We focus on state-of-the-art relativistic many-body calculations for the Yb atom's ground- and excited-state and the YbLi$^+$ potential energy surface. For that purpose, we exploit various quantum many-body methods, namely a spin-free and four-component implementation of the coupled cluster singles and doubles (CCSD) model and its equation of motion extensions, spin-free complete active space self-consistent field, and internally contracted multi-reference (MR) configuration interaction approaches, and spin-free MRCCSD with a perturbative and full triples correction. We oppose scalar relativistic calculations to four-component variants to support the reliability of our EOM-CCSD study and shed new light on the interplay between these systems' spin-orbit coupling and the proper treatment of relativistic effects. Most importantly, we observe a significant shift in the electronic spectra of the $f\rightarrow d$ excitation block. We also provide new reference potential energy surfaces for ground and excited states for which theoretically sound elastic scattering and pre-dissociation lifetimes are calculated. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2407_17224 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Changing the paradigm in f-containing cold molecules: the impact of spin-orbit coupling and f-d transitions on quasi-bound vibrational states Gałyńska, Marta de Moraes, Matheus M. F. Tecmer, Paweł Boguslawski, Katharina Atomic Physics Chemical Physics Present-day state-of-the-art ab initio many-body calculations on f-block containing cold molecules heavily focus on perturbative approaches for spin-orbit coupling and exclude a substantial part of the atomic transitions in the $f$- and $d$-shell. Here, we demonstrate the cruciality of a proper relativistic treatment of the $f$- and $d$-shell in Yb-containing diatomics and the inclusion of $f\rightarrow d$ transitions to obtain physically sound elastic scatterings and pre-dissociation lifetimes. We focus on state-of-the-art relativistic many-body calculations for the Yb atom's ground- and excited-state and the YbLi$^+$ potential energy surface. For that purpose, we exploit various quantum many-body methods, namely a spin-free and four-component implementation of the coupled cluster singles and doubles (CCSD) model and its equation of motion extensions, spin-free complete active space self-consistent field, and internally contracted multi-reference (MR) configuration interaction approaches, and spin-free MRCCSD with a perturbative and full triples correction. We oppose scalar relativistic calculations to four-component variants to support the reliability of our EOM-CCSD study and shed new light on the interplay between these systems' spin-orbit coupling and the proper treatment of relativistic effects. Most importantly, we observe a significant shift in the electronic spectra of the $f\rightarrow d$ excitation block. We also provide new reference potential energy surfaces for ground and excited states for which theoretically sound elastic scattering and pre-dissociation lifetimes are calculated. |
| title | Changing the paradigm in f-containing cold molecules: the impact of spin-orbit coupling and f-d transitions on quasi-bound vibrational states |
| topic | Atomic Physics Chemical Physics |
| url | https://arxiv.org/abs/2407.17224 |