Chapter 16

Spin in DFT

So far, we have mostly ignored the spin of the electrons, except for occasionally adding
factors of 2 in some places. However, in practice the spin is very important, and we have
now reached a point where it is appropriate to discuss how to include it properly into our
DFT framework.
In general, a full, rigorous treatment of spin is quite complicated, with lots of rules
and technicalities. We obviously don’t want to do this here (this would require a full
discussion of angular momentum and magnetism). Instead, we cover this topic only to
the extent that you can see what people actually do in practice when they carry out DFT
calculations with spin.

16.1 Spin-unpolarized and spin-polarized systems

We consider, as before, systems of N electrons, and we now explicitly indicate that the
total number of electrons is given by the sum of spin-up and spin-down electrons:

N = N↑ + N↓ . (16.1)

When there are different numbers of spin-up and spin-down electrons,

N↑ 6= N↓ , then we say that the system is spin-polarized.
When there are as many spin-up electrons as there are spin-down elec-
trons, N↑ = N↓ , then we say that the system is spin-unpolarized.

Let us look at two examples. Figure 16.1 shows schematic illustrations of the helium
atom (N = 2) and the lithium atom (N = 3). The He atom is spin-unpolarized, and the
Li atom is spin-polarized:

He: N↑ = 1, N↓ = 1 =⇒ N =1+1=2
Li: N↑ = 2, N↓ = 1 =⇒ N =2+1=3

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 ↑
↑
↑

+2 +3

↓
↓
Li
He

Figure 16.1: Schematic illustrations of the helium and lithium atoms. The He atom has
a closed shell and the spins are paired up. The Li atom has an unpaired spin.

Here, the He atom has a filled 1s shell, with an even number of electrons. The Li atom
has a filled 1s shell and one 2s outer electron, and the total number of electrons is odd.
There are a few general rules:

ˆ All atoms and molecules with an odd total number of electrons N are
spin-polarized.
ˆ All spin-unpolarized atoms and molecules have even numbers of elec-
trons N .
ˆ There are cases of atoms and molecules with even N that are spin-
polarized; this happens when they have open inner shells. Prominent
examples are the 3d transition metals Fe (N = 26) and Ni (N = 28).

So far, we have been talking about the ground state of atoms and molecules with a
given number N of electrons. When it comes to solids, we enter the field of magnetism.
You may know that there are materials which are magnetic and materials which are not.
The electronic spin is closely related to the magnetism of materials, see Fig. 16.2.

The electronic spin gives rise to a magnetic moment, and hence to a mag-
netic field. If an atom, molecule or solid is spin-polarized, it is magnetic.
A spin-unpolarized system, on the other hand, is nonmagnetic.

16.2 The Pauli equation, magnetic fields, and spin

orbitals
When you take an advanced course in quantum mechanics, you learn that the spin of
the electron is a relativistic phenomenon. In other words, the spin emerges naturally in
a formulation of quantum mechanics in which the special theory of relativity is properly
taken into account. Of course, we will not go into such depths here.

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 Figure 16.2: Magnetic moment of the electronic spin, giving rise to a magnetic field.

Instead, we directly write down (without proof) the generalization of the Schrödinger
equation where the spin shows up explicitly. This equation is called the Pauli equation,
and for a one-electron system (N = 1) it looks like this:
 2 2
~∇

− + V (r) + µB Bz σ̂z ψ(r) = Eψ(r) . (16.2)
2m
What is new here is that there is an externally applied magnetic field along the z-direction,
with field strength Bz . This magnetic field couples to the electronic spin, and it does so
through σ̂z , which is defined as
Ŝz = ~σ̂z /2 , (16.3)
where Sz is the z-component of the electronic spin. Furthermore, µB = e~/2m is a
constant known as the Bohr magneton. Strictly speaking, both σ̂z and Ŝz are operators
in “spin space”, but we don’t really need to worry about these technical details, as you
will now see.
How do you solve the Pauli equation, Eq. (16.2)? By writing the wave function as
 
ψ↑ (r)
ψ(r) = . (16.4)
ψ↓ (r)

The wave function ψ(r) has two components: one for spin-up and one for
spin-down. We write them as ψσ (r), where σ =↑, ↓ is the label for spin-up
and spin-down. We then rewrite the Pauli equation as two equations, one
for the spin-up and one for spin-down component.

 2 2
~∇

− + V (r) + µB Bz ψ↑ (r) = E↑ ψ↑ (r) (16.5)
2m
 2 2
~∇

− + V (r) − µB Bz ψ↓ (r) = E↓ ψ↓ (r) (16.6)
2m
So, you can see that the Pauli equation decouples into two independent equations for the
spin-up and the spin-down component. Some remarks:

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 ˆ When you compare Eqs. (16.5) and (16.6), you find that

E↑ − E↓ = 2µB Bz . (16.7)

In other words, there is a splitting between the energy levels of the spin-up and the
spin-down electron. This is called the Zeeman effect, as illustrated in Fig. 16.3.

↑
↑↓ 2 µ B Bz
↓

Bz = 0 Bz ≠ 0

Figure 16.3: Zeeman effect: a static magnetic field causes an energy level to split.

ˆ The decoupling of the Pauli equation into the two independent equations (16.5) and
(16.6) is only possible for the one-electron case, where the magnetic field is uniform
and along the z-direction. We’ll see in the next section how things work in Kohn-
Sham systems with N electrons (it turns out that there will be two equations for
the two components, but they will be coupled).

ˆ The spin-up and spin-down components, ψ↑ (r) and ψ↓ (r), are called spin orbitals.
Their physical interpretation is via the absolute square:

n↑ (r) = |ψ↑ (r)|2 , n↓ (r) = |ψ↓ (r)|2 , (16.8)

which gives the probability of finding a spin-up and a spin-down electron, respec-
tively, at position r.

16.3 The spin-dependent Kohn-Sham equation

We introduced Kohn-Sham theory in Chapter 11. The Kohn-Sham equation, Eq. (11.14),
was given without any reference to spin. The generalization of the Kohn-Sham equation
including spin is as follows:
∇2
 
− + Vsσ [n↑ , n↓ ](r) ϕjσ (r) = εjσ ϕjσ (r) , σ =↑, ↓ . (16.9)
2
This means that there are two Kohn-Sham equations: one for spin-up (σ =↑) and one for
spin-down (σ =↓). The Kohn-Sham orbitals ϕjσ (r) and eigenvalues εjσ now have a spin

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index. Explicitly, we have

∇2
 
− + Vs↑ [n↑ , n↓ ](r) ϕj↑ (r) = εj↑ ϕj↑ (r) , (16.10)
2
∇2
 
− + Vs↓ [n↑ , n↓ ](r) ϕj↓ (r) = εj↓ ϕj↓ (r) . (16.11)
2

The total density is given as the sum of spin-up and spin-down densities:
X
n(r) = n↑ (r) + n↓ (r) = nσ (r) (16.12)
σ=↑,↓

where
Nσ
X
nσ (r) = |ϕjσ |2 , σ =↑, ↓ . (16.13)
j=1

Remember, the total number of electrons is N = N↑ + N↓ .

Before doing a spin-polarized Kohn-Sham calculation for an N -electron

system, you need to specify how many of the electrons are spin-up and
how many are spin-down, i.e., you need to fix N↑ and N↓ .
Usually this choice is pretty obvious, but sometimes N↑ and N↓ are not a
priori known, and you need to try out different possibilities (for a given
total N ) to find out which one gives the lowest ground-state energy.

The Kohn-Sham effective potential in Eq. (16.9) is given by

n(r0 )
Z
Vsσ [n↑ , n↓ ](r) = Vσ (r) + dr0 + Vxcσ [n↑ , n↓ ](r) . (16.14)
|r − r0 |

Compared with the earlier expression for spin-unpolarized systems, Eq. (11.12), we notice
several important points.
First of all, the external potential Vσ (r) now carries a spin index. This means that
we allow for the possibility that there are different external potentials acting on spin-up
and spin-down electrons. For example, when considering an atom in a uniform magnetic
field, the spin-dependent total external potential is
Z Z
V↑ (r) = − + µB Bz , V↓ (r) = − − µB Bz . (16.15)
r r
In the absence of any externally applied magnetic fields, we will have V↑ (r) = V↓ (r).
n(r0 )
The next important point is that the Hartree potential, VH (r) = dr0 |r−r
R
0 | , does not

depend on the spin. It only depends on the total density n(r), and acts on the spin-up
and spin-down Kohn-Sham orbitals in the same way.

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 Lastly, the exchange-correlation potential Vxcσ [n↑ , n↓ ](r) is now formally given as a
functional of the spin-up and spin-down densities. In fact, we have

δExc [n↑ , n↓ ]
Vxcσ [n↑ , n↓ ](r) = , σ =↑, ↓ . (16.16)
δnσ (r)

This means that the exchange-correlation energy Exc [n↑ , n↓ ] is now a functional of the
spin densities n↑ and n↓ .

The two Kohn-Sham equations for spin-up and spin-down, Eqs. (16.10)
and (16.11), are coupled, since the Hartree and exchange-correlation po-
tentials depend on both n↑ (r) and n↓ (r). Thus, they have to be solved
self-consistently together.

The spin-dependent Kohn-Sham formalism ultimately follows from the extension of

the Hohenberg-Kohn theorem to spin-dependent systems. Everything is a functional of
n↑ (r) and n↓ (r). We will not prove this explicitly; the Hohenberg-Kohn proof goes through
pretty much in the same way as in Chapter 8.

16.4 The Local Spin-Density Approximation (LSDA)

We introduced the LDA for spin-unpolarized systems in Chapter 15. Let us now discuss
its generalization to spin-polarized system, the local spin-density approximation (LSDA).
To define the LSDA, we need a new reference system: the spin-polarized homogeneous
electron gas.

16.4.1 The spin-polarized homogeneous electron gas

Recall the jellium model and the homogeneous electron gas, presented in Chapter 14. Let
us assume, to begin with, that the electron gas is noninteracting.
Figure 16.4 shows, on the left-hand side, the energy dispersion of the spin-unpolarized
noninteracting electron gas, ε(k) = k 2 /2, which has the form of a parabola. In fact, there
is a separate parabola for spin-up and another one for spin-down electrons, but they are
on top of each other. The Fermi energy εF indicates the highest occupied energy. All
states below εF are occupied, all states above it are empty.
Now imagine that there is a uniform magnetic field Bz . According to the Pauli equa-
tion, discussed in Section 16.2, this gives rise to a Zeeman splitting of the energy levels. As
shown on the right-hand side of Fig. 16.4, this causes the spin-up electron gas parabola
to lie higher than the spin-down parabola. As a consequence, there is a smaller piece
of the ↑-parabola and a bigger piece of the ↓-parabola below εF . Thus, there will be

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 ε (k ) ε (k )

↑↓ ↑
εF εF
2 µ B Bz ↓

k k

Figure 16.4: Energy dispersions of the spin-unpolarized and spin-polarized electron gas.

more ↓-electrons than ↑-electrons. If the magnetic field changes sign, then the situation
is reversed between ↑ and ↓.

The spin-polarized homogeneous electron gas is characterized by just two num-

bers: n̄↑ and n̄↓ , the uniform densities of spin-up and spin-down electrons.

Instead of using n̄↑ and n̄↓ as the basic variables for the spin-polarized electron gas,
we can also use the total density,
n̄ = n̄↑ + n̄↓ , (16.17)

and the spin polarization,

n̄↑ − n̄↓
ζ̄ = . (16.18)
n̄↑ + n̄↓
The spin polarization is a dimensionless number, where −1 ≤ ζ̄ ≤ 1.

16.4.2 Exchange and correlation in LSDA

In LSDA, the exchange-correlation energy is approximated as
Z
Exc [n↑ , n↓ ] = dr ehxc n↑ (r), n↓ (r) ,
LSDA


(16.19)

where ehxc (n̄↑ , n̄↓ ) is the exchange-correlation energy density of the spin-polarized homo-
geneous electron gas. The spin-polarized exchange-correlation potential then follows as

dehxc (n̄↑ , n̄↓ ) 


LSDA
Vxcσ (r) =  n̄↑ =n↑ (r) , σ =↑, ↓ . (16.20)
dn̄σ
n̄↓ =n↓ (r)

So, all we need is explicit formulas for ehxc (n̄↑ , n̄↓ ). We will not derive them here, because
this becomes a bit tedious; we just quote some results.

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 1
0.9
0.8
0.7
0.6

f(zeta)
0.5
0.4
0.3
0.2
0.1
0
−1 −0.5 0 0.5 1
zeta

Figure 16.5: Interpolation factor f (ζ̄).

The exchange energy density of the spin-polarized homogeneous electron gas has the
following form:
ehx (n̄, ζ̄) = ehx (n̄, 0) + [ehx (n̄, 1) − ehx (n̄, 0)]f (ζ̄) , (16.21)

with the unpolarized (ζ̄ = 0) and the fully polarized (ζ̄ = 1) exchange energy densities
 1/3  1/3
3 3 3 6
ehx (n̄, 0) =− n̄4/3 , ehx (n̄, 1) =− n̄4/3 . (16.22)
4 π 4 π

The interpolation function f (ζ̄) is given by

(1 + ζ̄)4/3 + (1 − ζ̄)4/3 − 2
f (ζ̄) = . (16.23)
2(21/3 − 1)

The function f (ζ̄) is plotted in Fig. 16.5. You can see that it has values between 0 and 1
(remember that the spin polarization ζ̄ has values between −1 and 1).
A similar generalization to the spin-polarized case exists for the correlation energy
density, Eq. (14.41), but we won’t quote it here because it is a bit lengthy. You can find
the explicit formula in the literature (see footnote 4 of Chapter 14).
How does the LSDA perform? As an example, Table 16.1 shows the magnetic moments
of ferromagnetic iron,1 cobalt and nickel. As you can see, the agreement with experiment
is excellent (note that there are two sets of experimental data, one of them including
subtle orbital magnetic effects which are not included in the LSDA).
Finally, a famous example where the LSDA completely fails: certain transition metal
oxides (such as manganese oxide MnO and copper oxide CuO) are antiferromagnetic
insulators, but LSDA predicts them to be metals. These materials are known to be
“strongly correlated”: their behavior is not well captured by DFT approximations based
on the electron gas. We will talk a bit more about strong correlation later.
1
Strictly speaking, the LSDA predicts a nonmagnetic ground state of Fe, so the ferromagnetic state is
not the state of lowest energy. But once you impose the ferromagnetic state, the numbers are very good.

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Table 16.1: Magnetic moment per atom of ferromagnetic metals (in units of µB )

LSDA Experiment (spin only) Experiment (spin + orbital)

Fe 2.15 2.12 2.22

Co 1.56 1.57 1.71
Ni 0.59 0.55 0.61

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