Reference Energies for Double Excitations: Improvement and Extension
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866910523549810688 |
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| author | Kossoski, Fábris Boggio-Pasqua, Martial Loos, Pierre-François Jacquemin, Denis |
| author_facet | Kossoski, Fábris Boggio-Pasqua, Martial Loos, Pierre-François Jacquemin, Denis |
| contents | In the realm of photochemistry, the significance of double excitations (also known as doubly-excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoretical chemistry point of view. Based on state-of-the-art electronic structure methods (such as high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve and expand our prior set of accurate reference excitation energies for electronic states exhibiting a substantial amount of double excitations [http://dx.doi.org/10.1021/acs.jctc.8b01205; Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 electronic transitions across 26 molecular systems that we separate into two distinct subsets: (i) 28 "genuine" doubly-excited states where the transitions almost exclusively involve doubly-excited configurations and (ii) 19 "partial" doubly-excited states which exhibit a more balanced character between singly- and doubly-excited configurations. For each subset, we assess the performance of high-order coupled-cluster (CC3, CCSDT, CC4, and CCSDTQ) and multiconfigurational methods (CASPT2, CASPT3, PC-NEVPT2, and SC-NEVPT2). Using as a probe the percentage of single excitations involved in a given transition ($\%T_1$) computed at the CC3 level, we also propose a simple correction that reduces the errors of CC3 by a factor of 3, for both sets of excitations. We hope that this more complete and diverse compilation of double excitations will help future developments of electronic excited-state methodologies. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2403_19597 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Reference Energies for Double Excitations: Improvement and Extension Kossoski, Fábris Boggio-Pasqua, Martial Loos, Pierre-François Jacquemin, Denis Chemical Physics Materials Science Strongly Correlated Electrons Nuclear Theory In the realm of photochemistry, the significance of double excitations (also known as doubly-excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoretical chemistry point of view. Based on state-of-the-art electronic structure methods (such as high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve and expand our prior set of accurate reference excitation energies for electronic states exhibiting a substantial amount of double excitations [http://dx.doi.org/10.1021/acs.jctc.8b01205; Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 electronic transitions across 26 molecular systems that we separate into two distinct subsets: (i) 28 "genuine" doubly-excited states where the transitions almost exclusively involve doubly-excited configurations and (ii) 19 "partial" doubly-excited states which exhibit a more balanced character between singly- and doubly-excited configurations. For each subset, we assess the performance of high-order coupled-cluster (CC3, CCSDT, CC4, and CCSDTQ) and multiconfigurational methods (CASPT2, CASPT3, PC-NEVPT2, and SC-NEVPT2). Using as a probe the percentage of single excitations involved in a given transition ($\%T_1$) computed at the CC3 level, we also propose a simple correction that reduces the errors of CC3 by a factor of 3, for both sets of excitations. We hope that this more complete and diverse compilation of double excitations will help future developments of electronic excited-state methodologies. |
| title | Reference Energies for Double Excitations: Improvement and Extension |
| topic | Chemical Physics Materials Science Strongly Correlated Electrons Nuclear Theory |
| url | https://arxiv.org/abs/2403.19597 |