Wigner self energy

We recently presented a correlation method based on the Wigner intracule, in which correlation energies are calculated directly from a Hartree-Fock waveftmction. We now describe a self-consistent form of this approach which we term the Hartree-Fock-Wigner method. The efficacy of the new scheme is demonstrated using a simple weight function to reproduce the correlation energies of the first- and second-row atoms with a mean absolute deviation of 2.5 m h. 

The nematic mean-field U, the molecule-field interaction potential, WE, and the induced dipole moment, ju d, are evaluated at different orientations using Equation (2.263), and then the coefficients of their expansion on a basis of Wigner rotation matrices can be calculated, according to Equation (2.268). The permittivity is obtained by a self-consistency procedure, because the energy WE and the induced dipole moment / md, as well as the reaction field contribution to the nematic distribution function p( l), themselves depend on the dielectric permittivity. 

Fig. 1 Asymptotic structure coefficients as(j8), c ks,xG ) crw03), a CS), and aKS gOS) as fimction of barrier height parameter )S =VW/eF, where W is the barrier height and eF the Fermi energy. Corresponding values of the Wigner-Seitz radius rs for jellium and structureless-pseudopotential models over the metallic range of densities are also given. The relationship between rs and ff is via self-consistent calculations in the local density approximation for exchange-correlation.

The calculation of the ground-state energy of the Wigner electron crystal necessitates the self-consistent solution of the Slater-Kohn-Sham equations for the Bloch orbitals of a single fully occupied energy band, since there is one electron per unit cell and one is concerned with the spin-polarized state [45], This was accomplished by standard computational routines for energy band-... 

From the density, it is now possible to construct the potential for the next iteration, and also to calculate total energies. During the self-consistency loop, we make a spherical approximation to the potential. This is because the computational cost for using the full potential is very high, and that the density converges rather badly in the corners of the unit cell. In order not to confuse matters with the ASA (Atomic Sphere Approximation) this is named the Spherical Cell Approximation (SC A) [65]. If we denote the volume of the Wigner-Seitz cell centered at R by QR, we have fiR = QWR — (4 /3), where w is the Wigner-Seitz radius. This means that the whole space is covered by spheres, just as in the ASA. We will soon see why this is practical, when we try to create the potential. 

One of the drawbacks of Brillouin-Wigner perturbation theory is that the expressions for the energy components in second order and beyond contain the exact energy in the denominator factors. The equations must therefore be solved iteratively until self-consistency is achieved. The generalized Brillouin-Wigner perturbation theory [21] has the advantage that the denominators can be factored from the sum-over-states formulae. 

Equation (4.190) has p roots of which we take only one. The exact energy, q, occurs in the denominator factors in eqs. (4.191) and (4.193). The eq. (4.190) must, therefore, be solved iteratively until self-consistency is achieved. These are the basic equations of the multi-reference configuration interaction method in a Brillouin-Wigner formulation in the case of a p state reference. 

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