Application Note

G. Magnetic Moment of Iron

Ferromagnetism has its quantum mechanic origin in the difference of spin-up and spin-down
electron densities. It is driven by a balance between a gain in exchange energy due to larger spin-
polarization and a loss in Coulomb repulsion and kinetic energy of the electron system. Spin-
density functional theory is able to predict magnetic moments with astounding accuracy. The
present case illustrates this capability for bulk iron.

Outline of Procedure
The computational procedure involves the following steps

• Retrieve structure of bulk iron

• Optimize structure of bulk iron using a spin-polarized Hamiltonian
• Analyze results
1. Retrieve Structure of Bulk Iron

At ambient conditions, the thermodynamically stable form of bulk iron crystallizes in the
body-centered cubic structure. A database search with INFO MATICA gives a structure, which
was measured at T=79 K with the entry number ICSD.64999. The reported lattice parameter
is a=2.8608 Å. Load the structure in the M EDEA window (in the database window, select lines,
right-click and “View”).

2. Optimize Lattice Parameters

With the crystal structure of bcc Fe in the MEDEA window as the active window (dark blue
top bar), we compute the lattice parameters and the internal parameters using V ASP. From
Tools in the MEDEA menu bar, select VASP 4.6 and invoke the V ASP 4.6 graphical user
interface by selecting VASP 4.6≫Run from the MEDEA tool bar.
From the first panel (Calculation), select Structure Optimization as type of calculation,
check  Relax atom positions,  Allow cell volume to change,
 Allow cell shape to change.
In other words, a full cell optimizations and
relaxation of the atom positions is selected. The
calculations are performed with the precision
“Accurate”. In the section Magnetism choose
Spin-polarized. Under the SCF tab, select a
k-spacing of 0.1 Å-1 and check the option
 Use odd size grids. Under the same tab,
tighten the SCF convergence to 1.0e-06. With
these parameters, launch the calculation.

Analyze Results

The computed lattice parameter is 2.8218 Å,

Copyright © Materials Design, Inc. 2002-2008 1
Materials Design Application Note Magnetic Moment of Iron

which is 1.4 % smaller than the experimental value. Possibly, the reason for this discrepancy
is the treatment of correlation in the generalized gradient approximation underlying the
present calculations. The GGA may underestimate the Coulomb repulsion of the localized 3d
electrons of iron.
Atomic partial charges (electron charges):
Atom s p d total
----- -------- -------- -------- --------
Fe1 0.277 0.275 5.865 6.418
Total magnetic moment: 2.1869 Bohr magnetons
Atomic partial magnetic moments (Bohr magnetons):
Atom s p d total
----- -------- -------- -------- --------
Fe1 -0.004 -0.027 2.258 2.227
The magnetic moments are reported in the Job.out file. The total computed magnetic
moment of the primitive cell is 2.1869 μB (Bohr magnetons), which is the difference between
the charge density of spin-up and spin-down electrons. This value is close to the
experimental result of 2.12 μ B. The deviation between the computed and experimental value
is 3.2 %.

VASP computes projected partial charges for each atom. In the case of bcc Fe, the s-, p-, and d-
charges are given together with the partial magnetic moments (that is the difference
between spin-up and spin-down partial charges). The magnetic moment is dominated by d-
electrons. The spin-polarization of the s- and p-electrons is opposite to that of the d-
electrons, which makes the d-moment larger than the total magnetic moment per atom.

Copyright © Materials Design, Inc. 2002-2008 2