The Nuts and Bolts of

First-Principles Simulation

3: Density Functional Theory

CASTEP Developers’ Group

with support from the ESF k Network

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Density functional theory
Mike Gillan, University College London

• Ground-state energetics of electrons in condensed matter

• Energy as functional of density: the two fundamental
theorems
• Equivalence of the interacting electron system to a non-
interacting system in an effective external potential
• Kohn-sham equation
• Local-density approximation for exchange-correlation
energy

CASTEP Workshop, Durham University, 6 – 13

December 2001
 The problem

• Hamiltonian H for system of interacting electrons acted on by electrostatic

field of nuclei:
H  T U V
with T kinetic energy, U mutual interaction energy of electrons, V interaction
energy with field of nuclei.
• To develop theory, V will be interaction with an arbitrary external field:
N
V   v(ri )
i 1
with ri position of electron i.

• Ground-state energy is impossible to calculate exactly, because of electron

correlation. DFT includes correlation, but is still tractable because it has the
form of a non-interacting electron theory.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Energy as functional of density: the first theorem

For given external potential v(r), let many-body wavefunction be . Then
ground-state energy Eg is:
Eg   H 0  V 
and the electron density n(r) by:
n(r )   n^ (r )  Theorem 1: It is impossible that
two different potentials give rise
where the density operator n^ (r ) is defined as: to the same ground-state density
N distribution n(r).
n(r )    (r  ri )
^
Corollary: n(r) uniquely
i 1
specifies the external potential
v(r) and hence the many-body
wavefunction  .

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Convexity of the energy (1)
Theorem 1 expresses convexity of the energy Eg as function of external potential.

Convexity means: For two external potentials v (0; r ) and v (1; r ) , go along linear
path v( ; r )  (1   v(0; r )   v(1; r ) between them; if E g ( ) is ground-state
energy for 0    1 , then:
Eg ( )  (1   ) Eg (0)   E g (1) .

Proof of E g ( )  (1   ) E g (0)   E g (1) follows from 2nd-order

perturbation theory:
dEg / d     ( ) V  0 ( )
2
 0 (  ) V  n (  )
d E g / d   2
2 
 0,
n0 E0 ( )  En ( )
with   ( ) and  n ( ) wavefns of ground and excited states, E0 ( ) and En ( )
their energies, andV  v (1)  v (0) .

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Convexity of the energy (2)
Theorem 1 is equivalent to saying that a change of external potential v(r )
cannot give a vanishing change of density n(r )

This follows from convexity. Convexity implies that dE g / d  at   0 is

less than dE g / d  at   1 . But dE g / d     V  0 , so that:
 0 (1) V  0 (0) <  0 (0) V  0 (0)

so that:
 dr v(r)n(1, r) <  dr v(r)n(0, r) .
Hence:

 dr v(r)n(r) < 0 ,
which demonstrates that n(r )  0 , and this is Theorem 1.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 DFT variational principle
the second theorem
Since ground-state energy Eg is uniquely specified by n(r), write it as Eg[n(r)]. It’s
useful to separate out the interaction with the external field, and write:
Eg [n(r )]   dr v(r )n(r )  F [n(r )] ,
Where F[n(r)] is ground-state expectation value of H0 when density is n(r).

Theorem 2 (variational principle):

Ground-state energy for a given v(r) is Proof: Let v(r) and v’(r) be two different
obtained by minimising Eg[n(r)] with external potentials, with ground-state
respect to n(r) for fixed v(r), and the energies Eg and Eg’ and ground-state
n(r) that yields the minimum is the wavefns  and  ' . By Rayleigh-
density in the ground state. Ritz variational principle:

Eg <  ' H 0  V  '   dr v(r)n '(r)  F[n '(r)] ,

Where n’(r) is density associated with  ' . This proves the theorem.
The usual assumptions of non-degenerate ground state is needed.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 The Euler equation
Write F[n(r)] as:
F [n]  T [n]  G[n] ,
where T[n] is kinetic energy of a system of non-interacting electrons whose density
distribution is n(r). Then:
E[n]   dr v(r ) n(r )  T [n]  G[ n] .
Variational principle:
 T G 
 E  0   dr v(r )     n(r ) ,
subject to constraint:   n(r )  n(r ) 

 dr  n(r)  0 .
Handle the constant-number constraint by Lagrange undetermined multiplier, and
get: T G
 v(r )   ,
 n(r )  n (r )
with undetermined multiplier  the chemical potential.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Kohn-Sham equation
Rewrite the Euler equation for interacting electrons:
T G
 v(r )  
 n(r )  n(r )
by defining veff (r )  v(r )   G /  n(r ) , so that:
T
 veff (r )  
 n(r )
But this is Euler equation for non-interacting electrons in potential veff(r), and must be
exactly equivalent to Schroedinger
2 equation:

  2   veff (r )     ,
with n(r) given by:
2m
n(r )  2    (r ) .
2

  
Then put n(r) back into G[n(r)] to get total energy:

Etot [n(r )]   dr v(r )n(r )  T [n]  G[n] .

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Self consistency
How to do DFT in practice???
• We don’t know G[n(r)], and probably never will, but suppose we know an
adequate approximation to it.
• Make an initial guess at n(r), calculate  G /  n (r ) and hence
veff (r )  v(r )   G /  n(r ) for this initial n(r).
• Solve the Kohn-Sham equation with this veff(r) to get the KS orbitals
and hence calculate the new n(r):
n '(r )  2    i (r ) |2 .
  
• The output n’(r) is not the same as the input n(r). So iterate to reduce residual:
1/2
n    dr n '(r )  n(r ) 
2
.
 
The whole procedure is called ‘searching for self consistency’.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Exchange-correlation energy

• We have already split the total energy into pieces:

Etot [n]   dr v(r )n(r )  F [n]

F [n]  T [ n]  G[ n]
• Now separate out the Hartree energy:
1 n(r )n(r ')
EH [n(r )]  e 2  dr dr ' .
2 |r r'|
• Then exchange-correlation energy Exc[n] is defined by:

Etot [n]   dr v(r )n(r )  T [n]  EH [n]  E xc[n] .

So far, everything is formal and exact. If we knew the exact Exc[n], then we could
calculate the exact ground-state energy of any system!

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Local density approximation

• There is one extended system for which Exc is known rather precisely: the uniform
electron gas (jellium). For this system, we know exchange-correlation energy per
electron  xc ( n) as a function of density n.
• Local density approximation (LDA): assume the xc energy of an electron at point r is
equal to  xc ( n(r )) for jellium, using the density n(r) at point r. Then total Exc for
the whole system is:

ExcLDA   dr n  r   xc (n(r ))

• Some kind of justification can be given for LDA (see xxxxxxx). But the main
justification is that it works quite well in practice.

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Kohn-Sham potential in LDA

The effective Kohn-Sham effective potential in general is:

G  EH  Exc
veff (r )  v(r )   v(r )  
 n(r )  n(r )  n(r )
The Hartree potential is:
 EH  1 2 n(r1 )n(r2 )  2 n(r ')
  e  dr1dr2   e  dr ' .
 n(r )  n(r )  2 r1  r2  r r'
Exchange-correlation potential in LDA:

vxc (r ) 
 n(r )  dr1 n(r1 ) xc (n(r1 ))   xc (n(r )) ,
Where:
d
 xc (n)   n xc (n) 
dn
So in LDA, everything can be straightforwardly calculated!

CASTEP Workshop, Durham University, 6 – 13

December 2001
 Useful references

Here is a selection of references that contain more detail about DFT:

• P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964)
• W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965)
• N. D. Mermin, Phys. Rev. 137, A1441 (1965)
• R. O. Jones and O. Gunnarsson, Rev. Mod. Phys., 61, 689 (1989)
• M. C. Payne, M. P. Teter, D. C. Allan, T. A. Arias and J. D. Joannopoulos, Re.
Mod. Phys., 64, 1045 (1992)

CASTEP Workshop, Durham University, 6 – 13

December 2001