The Spin-Partitioned Total-Position Spread Tensor: An Application To Diatomic Molecules
| Autor: | Oriana Brea, Muammar El Khatib, Stefano Evangelisti, Celestino Angeli, Gian Luigi Bendazzoli, Thierry Leininger |
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| Přispěvatelé: | Groupe Méthodes et outils de la chimie quantique (LCPQ) (GMO), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Dipartimento di Chimica Fisica e Inorganica, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara (UniFE), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC) |
| Rok vydání: | 2016 |
| Předmět: |
Position Spread Tensor
Diatomic Molecules 010304 chemical physics Chemistry Ionic bonding 010402 general chemistry Total position spread 01 natural sciences Diatomic molecule Full configuration interaction Molecular physics ab initio Methods NO 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Diatomic Molecules Position Spread Tensor ab initio Methods Delocalized electron Chemical bond Computational chemistry 0103 physical sciences Molecule Tensor Physical and Theoretical Chemistry ComputingMilieux_MISCELLANEOUS |
| Zdroj: | Journal of Physical Chemistry A Journal of Physical Chemistry A, American Chemical Society, 2016, 120 (27), pp.5230-5238. ⟨10.1021/acs.jpca.6b01043⟩ |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.6b01043⟩ |
| Popis: | The spin partition (SP) of the total-position spread (TPS) tensor is applied to the case of a few light diatomic molecules at full configuration interaction (FCI) level. It appears that the SP-TPS tensor gives informations that are complementary with respect to the corresponding spin-summed (SS) quantity. The spin-summed total position-spread tensor (SS-TPS, Λ) is defined as the second moment cumulant of the total position operator, and the SP-TPS is its partition in equal (Λαα+ββ) and different spin (Λαβ+βα) contributions. Then, the SS-TPS allows description of the molecule charge mobility, while the SP-TPS allows description of the spin delocalization. The most relevant Cartesian-component for both tensors (SS-TPS and SP-TPS) is the component along the chemical bond (Λ(∥)), and it was found that its behavior was related to the type of interaction involved. For covalent bonds the SP-TPS has a squared growth when the bond is stretched, while for ionic bonds there exists a faster-than-linear growth after the avoided-crossing between the covalent and the ionic states. Other exotic bonds, like He2 and Be2, were also considered, and a particular spin delocalization was able to describe the different character of the two weakly bonded molecules, and specially the multireference character of the wave function along the dissociative potential energy curve. |
| Databáze: | OpenAIRE |
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