DENSITY FUNCTIONAL THEORY AND

TOTAL ENERGY CALCULATIONS

Introductory remarks
The precursor of any atomistic modeling is knowledge of the dependence of the
potential energy, E p , of the system studied on the positions, ri , of the particles that
form the system. Depending on the approach used when evaluating E p , this energy
may also be an explicit function of the total volume of the system. Hence, in general,
E p = E p (r1 ,r2 ,.....,rN ,V) . As explained in the Chapter dealing with the general
aspects of computer modeling, due to the translational invariance of the energy, E p
may depend only on the relative positions of the particles forming the system, i. e. on
the vectors ri ! rj = rij .
A fundamental description of the potential energy of a system of atoms must be based
on understanding the electronic structure of the system since bonding between atoms
is always mediated by the electrons. In general, E p is composed of the energy
associated with the electrons that provide the bonding and the interaction energy of
the nuclei. The sum of these two contributions is often called the total energy of the
system. In this chapter we discuss the so called ab-initio calculations of the total
energy. Most generally, such calculations are based on the fundamental quantum
mechanics (Schrdinger equation) when determining the energy associated with
electrons. Atomic numbers of the constituent atoms, and possibly some very basic
structural information, are the only empirical input. Such calculations are routinely
performed in the framework of the density functional theory in which the very
complex many-body problem of interacting electrons is replaced by an equivalent but
much simpler problem of a single electron interacting with an effective potential1.
The density functional theory approach is the most fundamental treatment presently
available in atomistic studies. It is applicable to all types of bonding. Any other,
more approximate schemes, are always applicable only to certain types of bonding,
such as metallic, covalent, ionic.
Born-Oppenheimer approximation
Since electrons are much lighter than nuclei their readjustment relative to the nuclei is
always much faster than the movement of the nuclei. Hence, the instantaneous
1

The Nobel Prize for Chemistry in 1998 was awarded for the development of this idea to W. Kohn
and J. Pople.

electron density is essentially the same as if all the nuclei were frozen in their
momentary positions. This is the basis of the Born-Oppenheimer approximation that
allows to separate the movement of electrons and nuclei (or ions). Electrons and
nuclei (or ions) are then considered as two autonomous systems the motions of which
are studied independently. This implies that forces on atoms, the calculation of
which requires, at least in principle, a fully quantum mechanical treatment of the
electronic structure, can be evaluated at any moment as if the nuclei (or ions) were in
fixed positions. The movement of atoms can then be studied in the framework of the
classical mechanics, for example using MD, with the forces determined for the
instantaneous configurations of atoms quantum mechanically.

Density functional theory2

Fundamental theorem of the density functional theory
The ground state energy of a many electron system is a functional of the charge
density, n(r) , and can be found by functional minimization of the energy of the
system with respect to n(r) . This means that the ground state energy does not depend
explicitly on the wave function of the system of electrons, !(" 1 ," 2 ,...," N e ) , where ! j
is the position of the jth electron and N e is the total number of electrons, but only on
their density
n(r) = N e " d! 2 " d! 3 ...." d! N e # (r, ! 2 ,...,! N e )#(r,! 2 ,...,! N e )
(DFT1)
The electron density of the ground state can then be determined by functionally
minimizing the energy of the system, E [n(r)] , with respect to n(r) and the
corresponding energy is the ground state energy.
The energy of a many electron system can then be written as

E !" n(r)#$ = E kin !" n(r)#$ + E ee !" n(r)#$ + E ext !" n(r) #$

(DFT2)

where E kin is the kinetic energy of the electrons, E ee the electron-electron interaction
energy and E ext the interaction energy between electrons and an externally applied
field. Assuming that the external field may be described by a potential Vext (r)

E ext = ! n(r)Vext (r)dr

Hohenberg and Kohn, Phys. Rev. B 136, 864, 1964.

(DFT3)

In a system of atoms Vext (r) is the potential describing the interaction between
electrons and nuclei. Its most general form is

Vext (r) = !$
j

Z je 2
4"#0 r ! rj

(DFT4)

Z j is the number of unit charges the magnitude of which is equal to the electronic
charge, e, associated with the nucleus j, rj is the position of this nucleus and ! 0 the
dielectric constant of the vacuum3. The summation extends over all the atoms.
However, a variety of approximations, such as the muffin-tin potential, various
pseudopotentials etc., have been used for the potential Vext. The total energy of the
system of fixed atoms, identified with its potential energy, E p , defined by equation
(G1), is then
Zi Z je2
1
E p = E !" n(r) #$ + 2 )
(DFT5)
i, j 4%&0 ri ' rj
i( j

where the second term on the right side of this equation is the interaction energy
between nuclei (ions) i and j. n(r) is determined by the functional minimization of
(DFT2). Note that n(r) depends on the positions of atoms since Vext (r) depends on
these positions.
While E ext in (DF2) is readily determined as a functional of n(r) according to
(DFT3), it is a major problem to ascertain the electron-electron interaction and the
kinetic energy of the electrons as functionals of n(r) . This problem is solved
differently in different schemes. In general, the idea is how best to express E ee and
Ekin as functionals of n(r) without solving the full many-body problem. If this can be
done, the problem of finding the ground state energy and electron density is reduced
to a problem of functional minimization of E [n(r)] with respect to n(r) .
Electron-electron interaction
The classical interaction energy between charges of the density n(r) is the Coulomb
type interaction

EH =

1 n(r)n(r!)
drdr!
2 "" r - r!

(DFT6)

In the following we use atomic units with e 4!"0 =1, ! = m = 1 ; the lengths are then in atomic
units (5.29x10-11m) and energy in Hartrees = 2Ry (4.36x10-18J).
3

This is called the Hartree energy. If E ee were identified with E H then the electronelectron interaction energy is overestimated for three reasons.
(i)
Owing to the Pauli exclusion principle the electrons are kept out of each other's
way. This leads to the lowering of the electron-electron interaction energy by
the so-called exchange energy.
(ii) The mutual electrostatic repulsion of electrons also keeps the electrons apart.
This repulsion lowers the electron-electron interaction energy even further.
The term describing this lowering is called correlation energy.
(iii) Even interaction of an electron with itself is included in E H while this should
be excluded.
The sum of the corrections which need to be added to (DFT6) is called the exchange
and correlation energy, E xc , and the electron-electron interaction energy is, therefore,

E ee = E H + E xc

(DFT7)

Some approaches also include so-called self-interaction correction mentioned in (iii).

Kinetic energy
The kinetic energy functional cannot be, in general, determined 'analytically' unlike
other parts of the energy. Approximations can be made, such as the Thomas-Fermi
model (see Appendix). However, within the density functional theory E kin !" n(r) #$ is
ascertained using the following argument.
First, the kinetic energy, E kin !" n(r) #$ , of the system of interacting electrons is
considered to be the same functional of the electron density as in the case of noninteracting electrons of the same density, E okin !" n(r) #$ .
The difference
o
E kin !" n(r) #$ % E kin !" n(r) #$ is usually small and it is assumed that this difference can be

included into the exchange and correlation energy, E xc [n(r)] . The energy of the
system of interacting electrons, written as the density functional, is then

E !" n(r)#$ = E okin !" n(r)#$ + % n(r) Vext (r)dr

+

1 n(r)n(r')
dr dr' + E xc !" n(r)#$
2 %% r & r'

(DFT8.1)

We now consider a fictitious system of non-interacting electrons of the same

density n(r) as the system studied, moving in an effective external potential Veff (r) .
At this stage neither Veff (r) nor n(r) are known and the goal is first to determine
Veff (r) . This step means that the electron-electron interaction becomes a part of the

effective potential and no direct interaction between electrons needs to be considered.

When this is done, the next step is to solve the simpler problem of non-interacting
electrons that move in the field defined by Veff (r) .
For the fictitious system of non-interacting electrons the total energy, written as the
density functional, is
o
o
E !" n(r)#$ = E kin !" n(r)#$ + % n(r)Veff (r)dr

(DFT8.2)

The requirement that the ground states of both functionals, E [n(r)] (equation
o
(DFT8.1)) and E [n(r)] (equation (DFT8.2)), have the same charge density leads to
the equation determining Veff by applying the variational principle to both of them.
The variation of E [n(r)] (DFT8.1) gives
o
!E "# n(r)$% = !E kin "# n(r)$% + & !n(r)Vext (r)dr +

!n(r)n(r')
&& r ' r' dr dr' + !Exc "# n(r)$% (DFT9.1)

where the last term is the functional variation of E xc (n(r)) . Similarly, the variation
o
of E [n(r)] (DFT8.2) yields
o
o
!E "# n(r)$% = !E kin "# n(r) $% + & !n(r)Veff (r)dr

(DFT9.2)

The variational problems !E [n(r)] = 0 and !E [n(r)] = 0 will be identical and yield
thus the same solution, n(r) , if
o

" !n(r)Veff (r)dr = " !n(r)Vext (r)dr + ""

!n(r)n(r#)
drdr# + !E xc %& n(r) '( (DFT10)
r $ r'

Since equation (DFT9.2) corresponds to the system of non-interacting electrons we

can write the charge density as

n(r) = " ! ! (r) ! ! (r)

(DFT11.1)

where ! ! (r) are one-electron wave functions and summation extends over all the
occupied states. If the system studied is not spin polarized, i. e. pairs of electrons
with opposite spins are in the same state,
M

n(r) = 2" ! ! (r) !! (r)

(DFT11.2)

!=1

where the summation extends over M lowest energy states; the factor of 2 arises
because each state is now occupied by two electrons. In the following we shall
always assume that the system studied is not spin polarized but spin polarization,
leading to magnetic effects, may be taken into account.

The variational condition (DFT9.2) expressed via Euler-Lagrange equation, leads to

the Schrdinger-like equation called Kohn-Sham equation
1 2
! " # ! (r) + Veff (r)# ! (r) = $ ! # ! (r)
(DFT12)
2
for the fictitious system of non-interacting electrons moving in an effective potential,
Veff . Its solutions are the one-electron wave functions ! ! (r) and associated
eigenenergies ! ! . However, unlike in the Schrdinger equation the potential Veff is
not given but it depends on the wave functions ! ! (r) and thus (DFT12) needs to be
solved self-consistently, as described below. The energy of this fictitious system of
non-interacting electrons is

o
kin

!" n(r) #$ + % n(r)Veff (r)dr = 2' &!

(DFT13)

!=1

The factor 2 again results from the spin degeneracy. Equation (DFT13) determines
the kinetic energy that can be inserted into equation (DFT8.1) for the energy of the
system of interacting electrons E [n(r)] . However, at this stage Veff is not yet known
explicitly and is only given implicitly by equation (DFT10). The difficulty is that the
exchange-correlation energy functional E xc (n(r)) is non-local and cannot be, in
general, written in the form " !n(r)F(r)dr , where F(r) is a function, which would
allow us to calculate Veff explicitly from equation (DFT10). For this reason
additional approximations, such as the local density approximation (LDA), need to be
introduced.

Local density approximation (LDA)

In the framework of LDA we assume that the exchange-correlation energy functional
is local and can be written as

E xc [n(r)] = ! n(r) " xc (n(r))dr

(DFT14)

where ! xc (n(r)) is the exchange and correlation energy per electron determined at a
point r by the electron density n(r) at this point and not non-locally by its
environment. In this case

!E xc (n(r)) = " xc (n(r))!n(r)dr

where

xc (n(r)) =

d {n(r)! xc (n(r))}
dn(r)

(DFT15.1)

(DFT15.2)

and it follows from equation (DFT10) that the effective potential entering the KohnSham equation (DFT12) is

Veff (r) = Vext (r) + #

n(r!)
d r! + xc (n(r))
r " r!

(DFT16)

Inserting equations (DFT16), (DFT14) and (DFT13) into equation (DFT8.1), the
energy of the interacting system of electrons is
M

E !" n(r)#$ = 2 & % ! '

!=1

1 n(r)n(r')
drdr'
2 (( r ' r'

(DFT17)

+ ( n(r) (% xc (n(r) ' xc (n(r))dr

The sum of the second and third term in this equation is commonly called the double
counting correction; it subtracts the Hartree energy and exchange-correlation energy
that are implicitly counted twice in the sum of the one-electron energies.
The exchange-correlation energy functional ! xc (n(r)) is not generally known for
spatially varying charge density. However, it can be evaluated highly accurately for a
jellium of uniform electron density and for this case it is possible to obtain ! xc (n(r))
as a function of an arbitrary uniform electron density. A common approximation is to
employ the exchange-correlation energy determined for the uniform electron density
in the case of non-uniform density.
Extensive calculations for solids, atoms and molecules employing the LDA
demonstrated its success. The reason is that the most important effect of the
exchange and correlation is the formation of an 'exchange-correlation hole' near each
electron that contains -1 electron (positive charge). This hole is not, in general,
spherically symmetric and its shape and size adjust according to the environment. In
the uniform electron gas this hole is spherical and this shape is, therefore, assumed in
the LDA. Hence, the shape of the hole is an approximation but it still includes -1
electron.
Evaluation of the effective potential Veff (r)
The effective potential Veff (r) (equation (DFT16)), which is needed when solving the
Kohn-Sham (Schrdinger-like) equation (DFT12), is itself a function of the charge
density (DFT11) determined by one-electron wave functions ! ! (r) that are solutions
of equation (DFT12). Thus the two equations, the Kohn-Sham equation (DFT12) and
equation (DFT16) for Veff (r) need to be solved self-consistently. This is what is
done in the so-called ab-initio calculations and the following flow chart summarizes
these procedures.

Choose a starting electron density n(r)

Construct the Hartree potential VH (r) = # n(r!) dr!

r " r!

This may be done by solving the Poissons equation

! 2VH = "4#n(r)

Construct Veff (r) = Vext (r) + VH + xc (n(r))

1
Solve ! "2 # ! (r) + Veff (r)# ! (r) = $! # ! (r)
2

Construct new electron density n(r) = 2" ! ! (r)! ! (r)

!=1

NO

Is the new n(r) the same as the input n(r) ?

YES

Calculation finished
finishedcomplete

Forces on atoms: The Hellmann-Feynman theorem

The force acting on an atom i is Fi = !grad r E p and thus to calculate the force we
i

need to evaluate the change of the total energy when an atom i is displaced by !ri .
The atomic coordinates are present explicitly in Vext (r) and in the term describing the
nuclei-nuclei interaction, which we call in the following E nn (see equations (DFT2, 4
and 5)). The differentiation of E nn is trivial but differentiation of E ext , which
contains Vext (r) (equation (DFT2)), is not straightforward. For this purpose let us
consider a change of the potential Vext (r) such that

Vext (r) ! Vext (r) + "Vext (r)

that induces a change in the charge density, !n(r) . In the framework of the density
functional theory the change in the total potential energy is

!Ep "# n(r) $% = !Ekin "# n(r)$% + !Eee "# n(r) $% + !Eext "# n(r) $% + !E nn (DFT18.1)
where

!E ext [n] = " !n(r)Vext (r)dr + " n(r)!Vext (r)dr

(DFT18.2)
The variational principle of the density functional theory says that for the ground
state the energy is at a minimum with respect to the variations in the charge (electron)
density and therefore
(DFT19)
!Ekin "# n GS (r)$% + !E ee "# nGS (r)$% + & !nGS (r)Vext (r)dr = 0
where n GS (r) is the ground state charge density. Combining equations (DFT19) and
(DFT18) gives
!E p [n GS ] = " n GS (r)!Vext (r)dr + !E nn
(DFT20)
The first term of the right hand side of this equation is the change in the electrostatic
energy due to the change in the external potential calculated for the fixed ground
state charge density of the electrons, n GS (r) . Hence, the force acting on the atom i is

Fi = !grad r E p = ! " nGS (r) grad r (Vext (r))dr ! grad r (E nn )

i

(DFT21)

The important result is that the force acting on an atom i does not depend on the
change in the electron density, !n(r) . But this result is only true when n(r) = nGS (r )
is the correct ground state density of electrons that corresponds to the exact
minimization of the density functional E p [n] . If the solution is not exact then

!Ekin "# n(r)$% + !E ee "# n(r)$% + & !n(r)Vext (r)dr ' 0 and this term contributes to the
forces. These forces are so called Poules forces.

10

Practical total energy calculations based on the LDA approximation

General formulation
In all methods of solving the Kohn-Sham equation, and subsequent calculation of the
total potential energy of a system of atoms, the one-electron wave functions are
always expanded into some chosen set of basis functions ! J (r) :
K

! ! (r) = # C J " J (r)

!

(DFT22)

J =1

where C J are expansion coefficients and K is the number of basis functions. At this
point the index J merely numbers the functions of the basis and is not related to atom
positions. When this expansion is inserted into the Kohn-Sham equation (DFT12) we
can transform the problem into the usual matrix formulation

#C (H
K

J =1

!
J

! " ! SLJ = 0

LJ

(DFT23)

where

1
H LJ = ! L " # 2 + Veff (r)! J
2
is the matrix element of the Hamiltonian and
SLJ = ! L ! J
is the overlap matrix3.

(DFT24)
(DFT25)

The eigenvalue problem (DFT23), which determines K eigenvalues of the

!
Hamiltonian, ! ! , and the corresponding coefficients C J (and thus the wave function

! ! (r) ), needs to be solved self-consistently since Veff (equation (DFT16)) depends

on the electron density
M

n(r) = 2" ! ! (r) ! ! (r) = 2" " C L C J # L (r)#J (r)

!

(DFT26)

! J ,L =1

where ! numbers different solutions of the Kohn-Sham equation and the summation
over ! extends over the occupied states. However, this form of the solution can be
23
sought for a cluster or a molecule but not for a bulk material containing ! 10 atoms.

! and ! ! , where ! and ! are wave functions

The meaning of the expressions !1 L
2
1
2
1
2

and L
an operator, is the usual one when using bra and ket notation
(r)dr and ! ! =
! L ! =
! (r)L!
! (r )! (r)dr .
3

"

All space

"

All space

11

In the case of the bulk, periodic boundary conditions have to be introduced as

described below.
Infinite periodic systems - Bloch's theorem
When dealing with a solid or liquid composed of a large number of atoms we employ
periodic boundary conditions and investigate thus a periodic system with a repeat cell
containing a finite number of non-equivalent atoms.
The repeat cell is either the unit cell of the structure studied (e. g. the repeat cell of
an ideal lattice) or a supercell constructed in accordance with the periodic boundary
conditions applied in the atomistic study. In the latter case the size of the repeat cell
is somewhat arbitrary and often dictated by the computational possibilities and
capabilities.
In periodic structures with translation vectors Tp , i. e. when Veff (r + Tp ) = Veff (r) , the
Bloch's theorem states that for any wave function !(r)

!(r + Tp ) = e

ik"Tp

!(r)

(DFT27)

where k is an arbitrary wave vector. This vector can be limited to the first
Brillouin zone of the periodic structure considered. An example of the first
Brillouin zone for the case of the body-centered-cubic structure in the real space is
shown below in Fig. 1.

Fig. 1. Brillouin zone for the body-centered-cubic structure.

12

Let us consider that the basis functions are centered, though not necessarily localized,
at atomic positions. Owing to the periodicity, every position vector can be written as
rj = rj0 + Tp , where rj0 is the position vector of the corresponding atom in the repeat
cell and Tp is a translation vector of the periodic structure. The basis function
centered at atom J can now be written as ! J (r) = ! j," (r # r j # Tp ) , where j labels
0

atoms within the repeat cell, labels other characteristics of these functions, such as
their symmetries (e. g. s, p, d, f functions) and Tp are various translation vectors.
The expansion of the one electron wave function ! ! (r) into the basis ! J (r) (DFT22)
is then

! ! (r) = % % C j," (rj + Tp )# j," (r $ rj $ Tp ) .

!

Tp j,"

When replacing r ! r + Tp" , where Tp! is another translation vector of the periodic
structure,

! ! (r + Tp" ) = & & C j,# (rj + Tp )$ j,# (r % rj % Tp + Tp" )

!

Tp

j,#

but since T! p = Tp ! Tp" is also a translation vector of the structure, we can sum over
T! p rather than Tp and, therefore,
!
0
" + T )$ (r % r 0 % T" ) .
! ! (r + Tp" ) = & & C j,# (rj + T
p
p"
j,#
j
p"
T" p

j,#

Following the Bloch's theorem

! ! (r + Tp" ) = e

ik#Tp"

! ! (r) = e

ik #Tp"

' 'C
Tp

!
j,$

(rj + Tp )% j,$ (r & rj & Tp )

j,$

Comparison of these two equations for ! ! (r + Tp" ) leads to

!

ik #Tp"

C j,! (rj + Tp + Tp " ) = e

C j,! (rj + Tp )

This equation is satisfied if

!

C j,! (rj + Tp ) = c j,! (k )exp[ik " (rj + Tp )]

where c !j,! (k ) depends only on the positions of atoms within the repeat cell, numbered
by j. However, it also depends on the vector k and, therefore, there is not just one set
of coefficients C !j,! but different sets of coefficients are obtained for different values
of the vector k.

13

The Bloch's theorem, which is a consequence of the translation symmetry, reduces

the dependence of the expansion coefficients on atom positions to the positions
within the repeat cell but introduces a new quantum number k. Thus, there is a whole
space of one-electron functions corresponding to different k-vectors, which will be
k
labeled in the following ! ! .
The expansion of such one electron function is then

! ! (r) = & & c j," (k )exp[ik # (rj + Tp )]$ j," (r % rj % Tp )

!

Tp

(DFT28.1)

j,"

We can introduce functions

k

! j," (r) =

& exp[ik # (r

0
j

+ Tp )]$ j," (r % rj % Tp )

(DFT28.2)

Tp

that are called Bloch's functions and we can write

! ! (r) = $ c j," (k)# j," (r)

!

j,"

Inserting this expansion into the Kohn-Sham equation (DFT12) yields

#c

!
j,!

j,!

k (r) = $ (k)# c! (k)"k (r)

(k )H"
j,!
!
j,!
j,!

(DFT29)

j, !

where the Hamiltonian

= ! 1 " 2 + V (r) .
H
eff
2

(DFT30)

The usual transformation leads to the eigenvalue problem determining ! ! (k ) and

!

c j,! (k )

#c
j,!

!
j,!

(k )H i,j (k ) = $ ! (k )# c j,! (k )Si, j (k )

",!

",!

(DFT31)

j,!

where the Hamiltonian matrix elements are

!,"
k
#k (r)
H i,j (k) = # i,! (r) H
j,"

(DFT32)

and the overlap integrals4

!,"

Si,j (k ) = # i,! (r) # j," (r)

4

(DFT33)

More detailed expression for the Hamiltonian matrix and for the overlap integrals are
! ,"
0
0
0
& (r $ r 0 $ T )
Hi, j (k ) = % exp[ik # (rj $ ri + Tp $ T! p )] & i ,! (r $ ri $ T! p ) H
j,"
j
p
!
Tp ,T
p

!,"
0
0
! )] & (r $ r 0 $ T
! ) & (r $ r 0 $ T )
Si, j (k) = % exp[ik # (rj $ ri + Tp $ T
p
i,!
i
p
j, "
j
p
!
Tp , T
p

! ,"

If the orbitals are orthonormal then S i , j (k) = # ij # !" .

14

If there are N a atoms in the repeat cell and n ! basis functions corresponding to
different parameters , then (DFT31) is the system of N a ! n " homogeneous
equations and the index ! denotes the corresponding solutions for a given vector k.
Hence, there are N a ! n " eigenvalues ! ! (k ) and corresponding sets of coefficients
!
c j,! (k ) and therefore there are N a ! n " one-electron wave functions

! k (r) = $ c j," (k)# j," (r)

!

(DFT34)

j,"

for each value of the wave vector k.

The eigenvalue problem must be solved for every vector k within the Brillouin zone5.
In practice we construct in the first Brillouin zone a mesh composed of N k k-points,
k m , and the solution is obtained for these k-vectors. The index ! then numbers
bands and ! ! (k ) is the k dependence of the energy of the ! th band. Plot of

! ! (k ) vs k displays the band structure for the studied case. However, such plot would
be surface in the four-dimensional space since k is a vector in the three-dimensional
reciprocal space. Hence, cross-sections of this plot along certain paths in the
Brillouin zone are always presented. An example is shown in Fig. 2.

Fig. 2. Calculated energy vs k dependence (band structure) for the bcc iron (with all
spins up) for paths H, HN, N and P shown in Fig. 1. EF is the Fermi energy and it
is set as zero level of energy.

When solving the eigenvalue problem for different k values we use the symmetry of the Brillouin
zone to reduce the amount of calculations. The simplest symmetry corresponds to the time reversal
and says that ! ! ("k ) = ! ! (k) .

15

Occupied states, charge density, Fermi energy, density of states

The occupied states, characterized by the quantum numbers k and ! , are those states the
energy of which is below the Fermi energy, E F , which is the highest energy
corresponding to an occupied state. The charge density is determined by the wave
!
functions ! k (r) of the occupied states, i. e.

n(r) = 2

"

! k (r) !k (r)

(DFT35)

!,k
occupied

or, when expressed via the Bloch basis functions !kj," (r) and corresponding expansion
coefficients c !j,! (k ) ,

n(r) = 2

$ $$ c

!
j,!

(k)ci," (k)# j,! (r) # i," (r)

(DFT36)

!,k
j,! i,"
occupied

However, the Fermi energy, E F , is not known a priori and needs to be determined. This
can be done most efficiently using the concept of the density of states.
The density of states, !(E) , is defined as the number of electronic states for which
! ! (k ) = E where k-vectors are continuously filling the first Brillouin zone. Hence,
mathematically it is defined as

!(E)=

2
"[E # $ ! (k )]dk
&
VBZ ! Over% BZ

(DFT37)

where VBZ is the volume of the Brillouin zone, the Dirac -function and the factor 2
again arises due to the spin degeneracy; the integration extends over all the k-vectors
in the first Brillouin zone.
If N e is the total number of electrons in the repeat cell then the Fermi energy is defined
by the relation
EF

Ne =

$ !(E)dE

(DFT38)

"#

Equation (DFT38) must then be solved for E F .

Example: Non-interacting, i. e. free electrons and the repeat cell in the form of a
parallelepiped.
In this case !(k) depends only on the magnitude of k and it is equal to the kinetic
energy of the electrons:
k2
!(k) =
2

16

The Brillouin zone is in this case also a parallelepiped and its volume is
3
VBZ = (2! ) V , where V is the volume of the repeat cell. Following equation (DFT37)

%
k2 (
!(E)= 3 + # ' E $ * dk
2)
4" Over BZ &
V

and by introducing spherical coordinates when dk = k sin !dkd!d" we obtain

!(E)=

V
4" 3

"

2"

kmax

- sin#d# - d$ -

'
k2 * 2
V
% ) E & , k dk = 2
2+
"
(

kmax

'
k2 * 2
% ) E & , k dk
2+
(

where k max is the largest magnitude of the vector k in the first Brillouin zone.

k2
dx
= x so that dk =
Substituting
2
2x

2V

x max

dx

2V

x max

% # E $ x x 2x = " 2 % # E $ x
"2 0
0
and by definition of the Dirac delta function6
1/ 2
V
!(E) = 2 2E
"
Since !(E) = 0 for E < 0, it follows from equation (DFT38) that
!(E)=

xdx

( )

Ne =
and, therefore,

EF =

2 2V 3/2
EF
3! 2

1
3! 2 "e
2

2/3

where !e is the density of electrons in the unit cell equal to N e / V.

Determination of the density of states and evaluation of E F in numerical
calculations
To evaluate the density of states we integrate equation (DFT37) numerically. For this
purpose we employ the same mesh composed of N k k-points, k m , in the first Brillouin
zone as when solving equations (DFT31). Similarly, we choose a small step in the
energy, !E , such that the energy will be considered the same within the interval
(E ! "E / 2, E + "E / 2) . Since the total volume of the Brillouin zone is VBZ , the

# ! ( a " x ) f(x)dx = f (a)

17

volume per one point of the k-mesh is

VBZ
Nk

. Equation (DFT37) can then be re-written

as

!(E) =

2
Nk

% {Number of " (k
km

) for which E # $E / 2 < " ! (k m ) < E + $E / 2

where the summation extends over all the points of the mesh. When the function !(E)
is known we determine E F by iteratively solving equation (DFT38). An example of the
density of states determined in this way is shown in Fig. 3 for the case of the bcc iron
for which the band structure is displayed in Fig. 2.

Fig. 3. Calculated density of states for the bcc iron with all spins up.
If we do not need to know the density of states but only seek E F , we can directly
evaluate the integral in (DFT38). The contribution of each state ( ! , k m ) to this integral
2
is
if ! ! (k m ) < E F and zero otherwise. Hence, the integral (DFT38) will give Ne if
Nk
N
we include e N k states for the vectors k m of the mesh that correspond to the lowest
2
values of ! ! (k m ) i. e. values of ! ! (k m ) associated with occupied states. The Fermi

18

energy, E F , is then identified with the value of the highest ! ! (k m ) from this set of
occupied states.
2
Example of non-interacting, i. e. free electrons. Since !(k) = k / 2 the occupied states
2

are all within the sphere of radius k F for which E F = k F / 2 ; k F is called the Fermi
vector. The number of such states is

1 4! 3
3
k F and since VBZ = (2! ) V ,
VBZ 3

1 4! 3
V 3
2
1/3
k F = 2 k F . This must be equal to Ne / 2 and thus k F = (3! "e )
and
VBZ 3
6!
2

E F = 1 2 (3! "e )

2 /3

Methods of DFT type calculations

The main distinguishing features of various methods of total energy calculations within
the density functional theory are the choice of the basis functions ! J (r) and potentials,
Vext, in which the electrons move. The 'best choice' depends on the type and size of the
system studied. For example, different choices are the best for simple metals, transition
metals, noble metals, semiconductors and insulators.
Examples of crystal potentials
Full potential: Complete crystal potential with no approximation of its shape (equation
DFT4).
Muffin-tin potential: A flat potential field into which is inserted a lattice of nonoverlapping spheres; inside the spheres the potential has an atomic-like form.
Pseudopotentials: The pseudopotential replaces the potential of an atom such that
outside the atomic core, where the electrons are tightly bound to the nucleus, it
reproduces the same electron density as the true atomic potential. The core electrons
are not treated explicitly and valence electrons move in the field of the pseudopotential.
These pseudopotentials are not weak and cannot be treated using the perturbation
theory.
Commonly used bases
(i) Plane waves and/or plane waves-like functions i.e. de-localized basis functions.
(ii) Atomic-like basis functions which are localized in the vicinity of individual atoms.
(iii) Wave functions developing self-consistently by analyzing scattering of an incident
wave by the crystal potential (KKR method).

19

Plane wave type basis functions

These are usually used in conjunction with pseudopotentials.
OPW:

Orthogonalized plane waves are wave functions constructed from plane

waves such that they are orthogonal to the core functions.

APW:

The plane waves in the constant potential region are augmented by atomictype functions to match the atomic-like solutions inside the muffin-tin
spheres.

Localized basis functions

LCAO:

Linear combination of atomic orbitals employs basis functions identical or

very similar to those obtained for the hydrogen atom.

LMTO:

Linearized muffin-tin orbitals are atomic-like orbitals of the muffin-tin

spheres rather than isolated atoms.

Some methods of calculation

FP-LMTO

The potential is not approximated and muffin-tin orbitals and Hankel

functions are used as the basis.

FP-LAPW

The potential is not approximated and linearized APWs are used as

basis.

LMTO-ASA

Linearized muffin-tin orbital method in the atomic sphere

approximation
It is assumed that each atom is at a center of a spherical effective potential well, the
atomic sphere, the volume of which is such that the volume of all the spheres just fills
the space. These spheres are, in general, overlapping so that the geometry is violated.
Relaxation calculations
When evaluating the total energy of a system for fixed positions of the nuclei (or atomic
cores) we find the ground state (minimum energy state) for the electrons. However, the
relaxation of the positions of atoms also lowers the energy of the system. This is in fact
the relaxation sought in atomistic studies which is the main theme of this course.
In principle, this can always be done by evaluating the Hellmann-Feynman forces,
which are then used in a simulation technique as forces acting on atoms. However,

20

direct calculation of these forces is not easy since the electron density must correspond
very accurately to the ground state i. e. Veff (r) has to be very accurately self-consistent.
It is common to carry out minimizations 'by hand' and the following are a few examples:
Calculations of the total energy as a function of atomic volume and/or other applied
strains. These calculations allow to determine the equilibrium lattice parameter and
elastic moduli. For example, the bulk modulus
d 2E p
B = !o
d! 2
where ! is the atomic volume and ! o the atomic volume in equilibrium. For instance,
the total energies of a number of transition metals was calculated as a function of the
volume per atom for various structures (Paxton, A. T., Methfessel, M. and Polatoglou,
H. M., Phys. Rev. B 41, 8127, 1990).
Calculations of the total energy as a function of several other parameters such as c/a
ratio in the hexagonal and tetragonal structures, which allow evaluation of equilibrium
characteristics of these lattices.
Calculations of energies of alternate crystal structures. For instance the total energies
for Si and Ge were calculated as functions of volume per atom for various structures
(Yin, M. T. and Cohen, M. L., Phys. Rev. B 26, 5668, 1982). This is one of the very
first LDA calculations of structural energy differences.
Calculation of the energy of an interface as a function of the relative displacement of the
adjoining grains which determines the most important relaxation mode.
Problems:

The cohesive energies are consistently overestimated in the LDA,

probably due to the error in calculation of the energy of free atoms.
The lattice parameter is consistently underestimated.
The bulk modulus is consistently overestimated.

However these under and overestimates are only up to 15% and usually much smaller.

21

EXAMPLES OF DFT-LDA STUDIES

Total energy (Ry/atom) for silicon and germanium calculated as a function of volume
(normalized to the experimental volume) for seven different crystal structures: diamond
cubic, hexagonal diamond (wurtzite), -tin, simple cubic, face-centered-cubic, bodycentered-cubic and hexagonal close-packed. The dashed line is the common tangent for
the diamond and -tin phases. At high pressures Si and Ge attain -tin phase. (Yin, M.
T. and Cohen, M. L., Phys. Rev. B 26, 5668, 1982; Phys. Rev. B 29, 6996, 1984).

22

The dependence of the binding energy (eV) on volume calculated for 3d transition
metals (Paxton, A. T., Methfessel, M. and Polatoglou, H. M. Phys. Rev. B 41, 8127,
1990) for the following structures: face-centered-cubic, body-centered-cubic, hexagonal
close-packed, simple hexagonal, simple cubic and diamond cubic. The volume is
normalized to the experimentally observed volume.

25

APPENDIX
THOMAS-FERMI MODEL
An approximate approach for determination of the kinetic energy as a function (not
functional) of the electron density is the Thomas-Fermi model that effectively uses
the LDA.
The kinetic energy is written as

E k [n ] = " ! k [n(r)]dr

where ! k [n(r) ] is the local kinetic energy. In the Thomas-Fermi approximation the
local kinetic energy is assumed to be equal to that of a homogeneous gas of noninteracting free electrons of density n.
Free electrons are described by plane waves and in a cubic box with the edge of size
L these waves are
1
!k (r) = 3/2 exp(ik " r)
L
3/2

where L is the normalization factor. Owing to the quantization, the volume of the
3
k -space occupied by one state is (2! L ) . The energy associated with a given state
of free electrons is just the kinetic energy
k2
E(k) =
2
The electrons occupy all the states up to the Fermi energy, E F , i. e. up to a maximum
value of k , called the Fermi vector, k F . Obviously

k 2F
EF =
2
and the total kinetic energy of all the electrons in the box is (using spherical
coordinates)
kF
k2 2
4!
E k = 2 " 4!
k dk = k 5F
2
5
0
The number of electrons inside the Fermi sphere is then
3
4!k 3F " L %
Ne = 2
$ '
3 # 2! &

26

The factor of two is in both cases introduced owing to the spin degeneracy. Since N e
3
is the number of electrons in the cube of the volume L the electron density is in this
case
N e k 3F
n= 3 = 2
L
3!
and, therefore, the kinetic energy density, ! k , is related to the electron density as
follows
2/3
12" 3
!k =
3" 2 ) n 5/3
(
5
In this model the exchange-correlation is neglected and the total potential energy is

E p !" n(r)#$ = & % k (n(r))dr + & n(r)Vext (r)dr +

1
2

&&

n(r)n(r ' )
r ( r'

drdr ' + E nn

This potential energy has to be functionally minimized with respect to the charge
density n(r) under the condition that the total number of electrons is conserved

! n(r) dr = N e
This leads to the Thomas-Fermi equation for n(r)
3

( )

4! 3!

2 2 /3

n(r)

2 /3

+ Vext (r) + $

n(r " )
r # r"

dr " # % = 0

where is the Lagrange multiplier, employed when minimizing E p [n(r)] ; it has the
meaning of the Fermi energy.
This equation has a moderate success, in particular for high densities of electrons.
The main drawbacks are the neglect of exchange-correlation and very approximate
estimate of the kinetic energy of electrons.