Hierarchy Configuration Interaction: Combining Seniority Number and Excitation Degree
| Autor: | Fábris Kossoski, Yann Damour, Pierre-François Loos |
|---|---|
| Přispěvatelé: | Groupe Méthodes et outils de la chimie quantique (LCPQ) (GMO), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), European Project: 863481,PTEROSOR |
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: |
Chemical Physics (physics.chem-ph)
Condensed Matter - Materials Science Nuclear Theory Strongly Correlated Electrons (cond-mat.str-el) Materials Science (cond-mat.mtrl-sci) FOS: Physical sciences Computational Physics (physics.comp-ph) Nuclear Theory (nucl-th) [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Condensed Matter - Strongly Correlated Electrons Physics - Chemical Physics General Materials Science Physical and Theoretical Chemistry Physics - Computational Physics |
| Zdroj: | Journal of Physical Chemistry Letters Journal of Physical Chemistry Letters, 2022, 13 (19), pp.4342-4349. ⟨10.1021/acs.jpclett.2c00730⟩ |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.2c00730⟩ |
| Popis: | We propose a novel partitioning of the Hilbert space, hierarchy configuration interaction (hCI), where the excitation degree (with respect to a given reference determinant) and the seniority number (i.e., the number of unpaired electrons) are combined in a single hierarchy parameter. The key appealing feature of hCI is that each hierarchy level accounts for all classes of determinants whose number share the same scaling with system size. By surveying the dissociation of multiple molecular systems, we found that the overall performance of hCI usually exceeds or, at least, parallels that of excitation-based CI. For higher orders of hCI and excitation-based CI, the additional computational burden related to orbital optimization usually do not compensate the marginal improvements compared with results obtained with Hartree-Fock orbitals. The exception is orbital-optimized CI with single excitations, a minimally correlated model displaying the qualitatively correct description of single bond breaking, at a very modest computational cost. Comment: 7 pages, 3 figures (supporting information available) |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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