Electron spin and magnetic structure

As an example of spin polarized calculations, we’ll study Fe(bcc) in a two-atom unit cell, i.e. a simple cubic Bravais lattice with a basis, where one Fe atom sits at the origin, the other in the middle of the unit cell. We’ll stick to the experimental lattice constant a = 2.87 Å. The atomic term of iron is [Ar]3d64s2, i.e. 8 valence electrons/atom is included in the calculation.

  • Use Hunds rule (maximum polarization rule) to calculate the magnetic moment of an isolated Fe atom. Draw schematically the one-electron eigenvalues for spin up and down on an energy axis, along with electron populations.
  • We’ll make three calculations for bulk iron:
    1. A non-magnetic calculation
    2. A ferro-magnetic calculation (aligned atomic moments)
    3. An anti ferro-magnetic calculation (antiparallel atomic moments).
  • How many bands are needed? Assuming the atoms polarize maximally (as the isolated atoms). For metals, always have at least 5 extra bands to allow for uneven filling of states for different k-points.
  • One should help a magnetic calculation by providing initial magnetic moments for the atoms using the magmoms argument to the Atoms constructor or by using the set_initial_magnetic_moments() method of the Atoms object. This is necessary to find magnetic states. Choose the magnetic moment close to the expected/desired magnetic state of your system (the experimental value is 2.22 per atom). The initial magnetic moment is relaxed during the self consistency cycles. Note that for a spin polarized calculation, each iteration step takes twice the time compared to a spin paired calculation.
  • For each of the three magnetic phases ferro, antiferro and nonmagnetic, write down sensible guesses for initial magnetic moment parameters: magnetic moment for each of the two atoms in the unit cell.

Start with this script: ferro.py.

Compare the energies of the three magnetic phases:

  • Experimentally, the ferromagnetic phase is most stable. Is this reproduced for LDA and GGA? Instead of repeating the three calculations using PBE, you can estimate the PBE numbers from the LDA densities you already have. This is done in this script: PBE.py.
  • Compare the calculated magnetic moment for the ferromagnetic phase with the experimental value. You can find the calculated value in the text output, or by using the get_magnetic_moments() method of the calculator object.