Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian - Archive ouverte HAL
Journal Articles Journal of Chemical Theory and Computation Year : 2021

Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian

Abstract

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- (CH3I, HX, and X-, X = Cl–At) and xenon-containing (Xe, XeF2) 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 (2DCM), 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 (2DCGM) are significantly more accurate than X2C calculations for which screened two-electron spin–orbit interactions are included via atomic mean-field integrals.
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Dates and versions

hal-03011292 , version 1 (15-07-2024)

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Loïc Halbert, Marta López Vidal, Avijit Shee, Sonia Coriani, André Severo Pereira Gomes. Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian. Journal of Chemical Theory and Computation, 2021, 17 (6), pp.3583-3598. ⟨10.1021/acs.jctc.0c01203⟩. ⟨hal-03011292⟩
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