Unscreened Hartree-Fock calculations for metallic Fe, Co, Ni, and Cu from ab-initio Hamiltonians

TL;DR

This paper presents the first unscreened Hartree-Fock calculations for metallic Fe, Co, Ni, and Cu using a quantum-chemical approach with Wannier functions, providing new insights into their electronic and magnetic properties.

Contribution

It introduces a novel ab-initio Hartree-Fock methodology for crystalline 3d transition metals, combining Wannier functions with a multi-band Hamiltonian approach.

Findings

HFA results lower total energies than LSDA

Exchange splitting and magnetic moments are slightly larger in HFA

d-bands sit lower within HFA compared to LSDA

Abstract

Unscreened Hartree-Fock approximation (HFA) calculations for metallic Fe, Co, Ni, and Cu are presented, by using a quantum-chemical approach. We believe that these are the first HFA results to have been done for crystalline 3d transition metals. Our approach uses a linearized muffin-tin orbital calculation to determine Bloch functions for the Hartree one-particle Hamiltonian, and from these obtains maximally localized Wannier functions, using a method proposed by Marzari and Vanderbilt. Within this Wannier basis all relevant one-particle and two-particle Coulomb matrix elements are calculated. The resulting second-quantized multi-band Hamiltonian with ab-initio parameters is studied within the simplest many-body approximation, namely the unscreened, self-consistent HFA, which takes into account exact exchange and is free of self-interactions. Although the d-bands sit considerably lower within HFA than within the local (spin) density approximation L(S)DA, the exchange splitting and magnetic moments for ferromagnetic Fe, Co, and Ni are only slightly larger in HFA than what is obtained either experimentally or within LSDA. The HFA total energies are lower than the corresponding LSDA calculations. We believe that this same approach can be easily extended to include more sophisticated ab-initio many-body treatments of the electronic structure of solids.