A numerical study of the extended Kohn-Sham ground states of atoms

Eric Cancès (1, 2) , Nahia Mourad (2)

1 MATHERIALS - MATHematics for MatERIALS
2 CERMICS - Centre d'Enseignement et de Recherche en Mathématiques et Calcul Scientifique

In this article, we consider the extended Kohn-Sham model for atoms subjected to cylindrically-symmetric external potentials. The variational approximation of the model and the construction of appropriate discretization spaces are detailed together with the algorithm to solve the discretized Kohn-Sham equations used in our code. Using this code, we compute the occupied and unoccupied energy levels of all the atoms of the first four rows of the periodic table for the reduced Hartree-Fock (rHF) and the extended Kohn-Sham Xα models. These results allow us to test numerically the assumptions on the negative spectra of atomic rHF and Kohn-Sham Hamiltonians used in our previous theoretical works on density functional perturbation theory and pseudopotentials. Interestingly, we observe accidental degeneracies between s and d shells or between p and d shells at the Fermi level of some atoms. We also consider the case of an atom subjected to a uniform electric-field. For various magnitudes of the electric field, we compute the response of the density of the carbon atom confined in a large ball with Dirichlet boundary conditions, and we check that, in the limit of small electric fields, the results agree with the ones obtained with first-order density functional perturbation theory.

Mots clés: density functional theory; electronic structure of atoms; extended Kohn–Sham model; Stark effect

Domaines: Physique mathématique [math-ph]

Eric Cancès, Nahia Mourad. A numerical study of the extended Kohn-Sham ground states of atoms. Communications in Applied Mathematics and Computational Science, 2018, 13 (2), pp.139-188. ⟨hal-01454677⟩