Exact two-component Hamiltonians for relativistic quantum chemistry - Archive ouverte HAL
Journal Articles The Journal of Chemical Physics Year : 2022

Exact two-component Hamiltonians for relativistic quantum chemistry

Abstract

Based on self-consistent field (SCF) atomic mean-field (amf) quantities, we present two simple yet computationally efficient and numerically accurate matrix-algebraic approaches to correct both scalar-relativistic and spin–orbit two-electron picture-change effects (PCEs) arising within an exact two-component (X2C) Hamiltonian framework. Both approaches, dubbed amfX2C and e(xtended)amfX2C, allow us to uniquely tailor PCE corrections to mean-field models, viz. Hartree–Fock or Kohn–Sham DFT, in the latter case also avoiding the need for a point-wise calculation of exchange–correlation PCE corrections. We assess the numerical performance of these PCE correction models on spinor energies of group 18 (closed-shell) and group 16 (open-shell) diatomic molecules, achieving a consistent [Formula: see text] Hartree accuracy compared to reference four-component data. Additional tests include SCF calculations of molecular properties such as absolute contact density and contact density shifts in copernicium fluoride compounds ([Formula: see text], n = 2,4,6), as well as equation-of-motion coupled-cluster calculations of x-ray core-ionization energies of [Formula: see text]- and [Formula: see text]-containing molecules, where we observe an excellent agreement with reference data. To conclude, we are confident that our (e)amfX2C PCE correction models constitute a fundamental milestone toward a universal and reliable relativistic two-component quantum-chemical approach, maintaining the accuracy of the parent four-component one at a fraction of its computational cost.
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Dates and versions

hal-03833593 , version 1 (28-10-2022)

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Stefan Knecht, Michal Repisky, Hans Jørgen Aagaard Jensen, Trond Saue. Exact two-component Hamiltonians for relativistic quantum chemistry. The Journal of Chemical Physics, 2022, 157 (11), pp.114106. ⟨10.1063/5.0095112⟩. ⟨hal-03833593⟩
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