Relativistic EOM-CCSD for core-excited and ...
Type de document :
Compte-rendu et recension critique d'ouvrage
DOI :
Titre :
Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian
Auteur(s) :
Halbert, Loïc [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
López Vidal, Marta [Auteur correspondant]
Danmarks Tekniske Universitet = Technical University of Denmark [DTU]
Shee, Avijit [Auteur correspondant]
Department of Chemistry [Ann Arbor]
Coriani, Sonia [Auteur correspondant]
Danmarks Tekniske Universitet = Technical University of Denmark [DTU]
Severo Pereira Gomes, Andre [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
Physico-Chimie Moléculaire Théorique [PCMT]
López Vidal, Marta [Auteur correspondant]
Danmarks Tekniske Universitet = Technical University of Denmark [DTU]
Shee, Avijit [Auteur correspondant]
Department of Chemistry [Ann Arbor]
Coriani, Sonia [Auteur correspondant]
Danmarks Tekniske Universitet = Technical University of Denmark [DTU]
Severo Pereira Gomes, Andre [Auteur correspondant]
Physico-Chimie Moléculaire Théorique [PCMT]
Titre de la revue :
Journal of Chemical Theory and Computation
Pagination :
3583-3598
Éditeur :
American Chemical Society
Date de publication :
2021-05-04
ISSN :
1549-9618
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Résumé en anglais : [en]
We report an implementation of the core–valence separation approach to the four-component relativistic Hamiltonian-based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD) for the calculation ...
Lire la suite >We report an implementation of the core–valence separation approach to the four-component relativistic Hamiltonian-based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD) for the calculation of relativistic core-ionization potentials and core-excitation energies. With this implementation, which is capable of exploiting double group symmetry, we investigate the effects of the different CVS-EOM-CCSD variants and the use of different Hamiltonians based on the exact two-component (X2C) framework on the energies of different core-ionized and -excited states in halogen- (CH<sub>3</sub>I, HX, and X<sup>-</sup>, X = Cl–At) and xenon-containing (Xe, XeF<sub>2</sub>) species. Our results show that the X2C molecular mean-field approach [Sikkema, J.; J. Chem. Phys. 2009, 131, 124116], based on four-component Dirac–Coulomb mean-field calculations (<sup>2</sup>DC<sup><i>M</i></sup>), is capable of providing core excitations and ionization energies that are nearly indistinguishable from the reference four-component energies for up to and including fifth-row elements. We observe that two-electron integrals over the small-component basis sets lead to non-negligible contributions to core binding energies for the K and L edges for atoms such as iodine or astatine and that the approach based on Dirac–Coulomb–Gaunt mean-field calculations (<sup>2</sup>DCG<sup><i>M</i></sup>) are significantly more accurate than X2C calculations for which screened two-electron spin–orbit interactions are included via atomic mean-field integrals.Lire moins >
Lire la suite >We report an implementation of the core–valence separation approach to the four-component relativistic Hamiltonian-based equation-of-motion coupled-cluster with singles and doubles theory (CVS-EOM-CCSD) for the calculation of relativistic core-ionization potentials and core-excitation energies. With this implementation, which is capable of exploiting double group symmetry, we investigate the effects of the different CVS-EOM-CCSD variants and the use of different Hamiltonians based on the exact two-component (X2C) framework on the energies of different core-ionized and -excited states in halogen- (CH<sub>3</sub>I, HX, and X<sup>-</sup>, X = Cl–At) and xenon-containing (Xe, XeF<sub>2</sub>) species. Our results show that the X2C molecular mean-field approach [Sikkema, J.; J. Chem. Phys. 2009, 131, 124116], based on four-component Dirac–Coulomb mean-field calculations (<sup>2</sup>DC<sup><i>M</i></sup>), is capable of providing core excitations and ionization energies that are nearly indistinguishable from the reference four-component energies for up to and including fifth-row elements. We observe that two-electron integrals over the small-component basis sets lead to non-negligible contributions to core binding energies for the K and L edges for atoms such as iodine or astatine and that the approach based on Dirac–Coulomb–Gaunt mean-field calculations (<sup>2</sup>DCG<sup><i>M</i></sup>) are significantly more accurate than X2C calculations for which screened two-electron spin–orbit interactions are included via atomic mean-field integrals.Lire moins >
Langue :
Anglais
Vulgarisation :
Non
Projet ANR :
Commentaire :
13 pages, 4 figures in main text, 7 figures in supplemental information
Source :
Fichiers
- http://arxiv.org/pdf/2011.08549
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- 2011.08549
- Accès libre
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