Lecture VIII DFT-3

A
very short introduction to

density functional theory (DFT)
FKA091 - Condensed matter physics

Lecturer: Paul Erhart, Department of Physics
Materials and Surface Theory Division, Origo, R7111
Overview
• What is density functional theory (DFT) good for?
• Basic considerations
HK
vext (r) n0 (r)
• Hohenberg-Kohn theorems
n ({r i }) 0 ({r i })
• Kohn-Sham equations and the exchange-correlation functional

✓ ◆
1 2
r + vext (r) + vH (r) + vxc (r) i (r) = ✏i i (r)
2
• Shortcomings of DFT
Erhart, FKA091 11/2016

Some possible applications of DFT
Structure prediction and phase stability: Platinum series nitrides
Forces à Vibrations
N dimer
Total energies Pt
Structure prediction and phase stability: Platinum series nitrides
Electronic structure
High pressure Low pressure
(single bonded nitrogen) (triple bonded nitrogen)
Defects: Thermodynamics, kinetics, electronic properties
Energetics – Which defects and how many
Vacancy level
Electronic structure
Total energies and forces à optical properties
Property prediction and screening: Substituted norbornadienes
donor
acceptor
Substitutions affect
position of absorption band
à can be tuned to solar spectrum
HOMO LUMO

Property prediction and screening: Substituted norbornadienes
Balance between computational effort

and accuracy/predictivness

• Enables calculation of total energies and forces

under very general conditions
– Structure prediction One of the standard
– Thermodynamics and kinetics computational tools in
condensed matter, chemistry,
and biochemistry in both
• Provides description of electronic structure academia and industry
– starting point for e.g., optical properties
• Good balance between accuracy/predictiveness and computational cost
– Scales N3 or better (N=number of electrons)
– Enables calculations with thousands of electrons
• Very well established technique
– Capabilities and limitations reasonably understood
– Efficient implementations available
FKA091: Density functional theory
Basic considerations
The Schrödinger equation
@
i = Ĥ nuclear R
@t electronic r
X ~2 X ~2
Ĥ = rn 2
r2i mixed
n
2M i
2me
| {z } | {z }
T̂R T̂r Kinetic terms
1 1 X Zn Zm e2 1 1X e2
+ +
4⇡✏0 2 |Rn Rm | 4⇡✏0 2 |r i r j |
n6=m i6=j
| {z } | {z }
V̂r V̂r
1 X Zn e2
+
4⇡✏0 i,n |r i Rn |
| {z }
V̂r,R Potential terms
The Schrödinger equation
@
i = Ĥ (r 1 , r 2 , . . . , R1 , R2 , . . . ; t)
@t
Wavefunction is a function of
coordinates of all electrons and ions
(and depends parametrically on time)
Ĥ = T̂r + T̂R + V̂r + V̂r,R + V̂R

= T̂R + V̂R + T̂r + V̂r + V̂r,R
nuclear electronic mixed
Notational convenience:
(r 1 , r 2 , . . . , R1 , R2 , . . . ; t) Density functional theory in a nut shell:
Reduce 3N-dimensional problem
= ({r i }, {Ri }; t) to a 3-dimensional one
= (r, R; t)
Born-Oppenheimer approximation
Expand many body wave function in a complete electronic basis set
that depends on positions of both nuclei and electrons
X
(r, R; t) = n (R; t) n (r, R)
n
Insert wave function ansatz into Schrödinger equation
@
i = Ĥ
@t
… and project onto the electronic basis: m (r, R)
@ ⇣ ⌘ X hD E i
i m = T̂R + V̂R m+ m (r, R) T̂r + V̂r + V̂R,r n (r, R) + V̂mn n
@t n
~2 ~2 ⌦ 2
↵
V̂mn = h m (r, R)|rRk | n (r, R)i · rRk + m (r, R)|rRk | n (r, R)
Mk 2Mk
V̂mn depends on derivatives of electronic states

with respect to nuclear positions and velocities
X
✏m (R) = h m (r; R)|T̂r + V̂r + V̂R,r | n (r; R)i
n
Rearrange terms
@ X
i m (R; t) = [T̂R + V̂R + ✏m (R)] m (R; t) + Vmn n (R; t)
@t n
… and choose a representation (the so-called adiabatic representation),

in which electronic wave function depends only parametrically
on the nuclear positions, i.e. m (r, R) ! m (r; R)
Born-Oppenheimer approximation = neglect of cross terms

The Born-Oppenheimer approximation enables separation
into two separate problems
1. The electron-structure problem: Regard the nuclei as fixed in space

and solve for the electronic degrees of freedom.
Ĥe m (r; R)
= ✏m (R) m (r; R)
X1 1 X e 2 X Zn
Ĥe = r2i +
i
2 2 |r i r j | i,n
|r i Rn |
i6=j
| {z } | {z } | {z }
Tˆr V̂r V̂r;R
2. The nuclear problem: Solve for the nuclear degrees of freedom using
the derived potential energy surface (PES).
@
i m (R; t) = [T̂R + V̂R + ✏m (R)] m (R; t)
@t
The Hohenberg-Kohn theorems

Schematic of Hohenberg-Kohn theorems
Hohenberg and Kohn, 1964 (HK):

a density functional theory as an exact theory of many-body systems
Ĥ = T̂r + V̂r + V̂r;R Reduction of dimensionality!
given an HK the ground state

external potential
vext (r) n0 (r) density
f=3 f=3
a solution to the the ground state

Schrödinger solution n ({r i }) 0 ({r i }) solution (lowest energy)
f=3N f=3N
Hohenberg-Kohn theorem #1
Theorem #1
• For any electronic system in an external potential
vext (r)
said potential is determined uniquely, safe for a constant,
by the ground state density n0 (r)
Corollary #1
• Since the Hamiltonian is thus fully determined, it follows that
the many-body wave functions for all states (ground and excited)
are determined.
• Thus all properties of the system are completely
determined given only the ground state density.

Hohenberg-Kohn theorem #1 – Proof
Let vext(r) be the external potential of a system, with associated ground state
density n(r), the total number of particles N, Hamiltonian H, and the ground
state wave function ψ and ground state energy E. v : H, n(r), , E, N
ext
Similarly consider a second system of N particles 0

vext 6= vext 0
+C 6= 0 vext : H 0 , n0 (r), 0
, E0, N
where and hence
Then by the variational principle

Z
E = h |H| i < h 0 |H| 0 i = h 0 |H 0 | 0 i + [vext (r) 0
vext (r)] n0 (r)dr
Z
= E0 + [vext (r) 0
vext (r)] n0 (r)dr
Z
H = T̂r + Vr + vext (R)n0 (r)
Z
H 0 = T̂r + Vr + 0
vext (R)n0 (r)

Hohenberg-Kohn theorem #1 – Proof
Z
Thus
E < E0 + [vext (r) 0
vext (r)] n0 (r)dr
… and conversely Z
E0 < E + 0
[vext (r) vext (r)] n(r)dr
Adding the inequalities gives Z

E + E0 < E + E0 + [vext (r) 0
vext (r)] [n0 (r) n(r)] dr
n0 (r) ⌘ n(r) is excluded as this would result in 0<0
Thus any potential except

vext (r) vext (r) + C
leads to n0 (r) 6= n(r) Q.E.D.

Theorem #2
• A universal functional of the energy can be defined in terms
E[n]
of the density , which is valid for any external potential
n(r) vext (r)
For any particular the exact ground state of the system
vext (r)
is determined by the global minimum value of this functional.
Corollary #2
• Said functional alone is sufficient to determine
the ground state energy and density.
• Excited states have to be determined by other means.
• DFT is a ground state theory
Thus by means of minimization, the

ground-state electron density can be found as
D E
E0 [n] = min |Ĥ| = min , min E[n]
!ñ !ñ ñ2N

For convenience separate the energy functional into
• and a universal part (independent on N, mass and charge of nuclei, etc)
• a system dependent part, i.e. depends on vext (r)
Energy functional: Z
E[n(r)] = F [n(r)] + vext (r)n(r)dr
universal system dependent
The universal functional contains the individual contributions of

kinetic energy, classical Coulomb interaction, and
the non-classical self-interaction correction
Z
1 n(r)n(r 0 ) 0 true
F [n(r)] = T [n(r)] + drdr + Exc
2 |r r 0 |

Some remarks
• The HK theorems can be generalized to include spin

(not magnetic fields)
• … reformulate the many-body problem in terms of the density

but do not actually solve it
• The HK functional is a priori unknown!

There is no direct link from the density to e.g., the kinetic energy.
• HK-DFT is in principle exact (no approximations) but impractical

à In practice one uses the Kohn-Sham approach

The Kohn-Sham equations

The Kohn-Sham ansatz
•  Kohn-Sham: replace the original many-body problem with an auxiliary
à Replace the original many-body problem with an
system of non-interacting particles.
auxiliary system of non-interacting particles.
Non-interacting
Interacting electrons auxiliary
+ real potential particles in an
effective potential
Assumption:
•  K-S assumes that the ground stateGround state density of interacting
density of the original interacting
system is equal
Walter Kohn Lu JeutoSham
that of some chosen non-interacting system that is
system is equal to that of some non-
exactly soluble, with all the difficult parts (exchange and
interacting system correlation)
that is exactly soluble,
included in some approximate functional of the density.
with all the difficult parts (exchange and
correlation) included in some
approximate functional of the density.
13. October 2010 6. The density functional theory 18
1998 (chemistry) Erhart, FKA091 11/2016

Independent particles approximations
• Hartree ansatz (r 1 , r 2 , . . . , rN ) = 1 (r1 ) 2 (r 2 ) . . . N (r N )
• Fock: does not satisfy anti-symmetry requirement (fermions)

à need to take Slater determinant
V. A. Fock
D. R. Hartree Erhart, FKA091 11/2016

Kohn-Sham ansatz
• In principle, the solution of the independent KS problem

determines all properties of the full many-body system.
HK Kohn-Sham
vext (r) n0 (r) n0 (r) vKS (r)
n ({r i }) 0 ({r i }) i=1...N (r)
The auxiliary Hamiltonian contains the usual kinetic energy term

and a local effective potential acting on the electrons

The Kohn-Sham energy functional
• In KS decomposition the total energy of a many
electron system in an external potential is
Z
E[n] = T0 [n(r)] + drn(r)vext (r) + EH [n(r)] + Exc (r)
N.B.: Here, we use atomic units. Erhart, FKA091 11/2016

For convenience separate the energy functional into
• and a universal part (independent on N, mass and charge of nuclei, etc)
• a system dependent part, i.e. depends on vext (r)
Energy functional: Z
E[n(r)] = F [n(r)] + vext (r)n(r)dr
universal system dependent
The universal functional contains the individual contributions of

kinetic energy, classical Coulomb interaction, and
the non-classical self-interaction correction
Z
1 n(r)n(r 0 ) 0 true
F [n(r)] = T [n(r)] + drdr + Exc
2 |r r 0 |

The Kohn-Sham energy functional
• In KS decomposition the total energy of a many
electron system in an external potential is
Z
E[n] = T0 [n(r)] + drn(r)vext (r) + EH [n(r)] + Exc (r)
kinetic external potential class. Coul. self-int.
“0” à non-inter-
acting particles
occ
X 2
n(r) = | i (r)| electron density
i
X Zn
vext = potential from the nuclei
n
r RI
Z Z 0
1 0 n(r)n(r )
EH [n] = drdr 0 classical Coulomb energy
2 |r r |
Z
Exc [n] = drn(r)"xc [n(r)] exchange and correlation
N.B.: Here, we use atomic units. Erhart, FKA091 11/2016
Kohn-Sham functional
• The KS decomposition separates contributions that are (in principle)
possible to compute from contributions that are much more complicated.
Jones, Gunnasson (1989)
kinetic Coulombic exchange-correlation (XC)
XC is on an absolute scale a minor contribution to the total energy.

It is crucial that the kinetic energy is evaluated to a high accuracy
(this is not done in Thomas-Fermi theory).
Kohn-Sham one-electron orbitals
• The one-electron orbitals (KS orbitals)

are solutions to the KS equation (one-particle equation!!)
✓ ◆
1 2
2
KS orbital
• It is tempting to treat these states as KS eigenenergy
proper electronic (quasi) particle states;
but beware, this are fictitious states
• Nonetheless band structures often useful;

although band gap underestimation is common

DFT in practice: The exchange-correlation functional
Z
✏xc
Exc [n] = drn(r)"xc [n(r)] vxc =
n
potential
Local density approximation (LDA)
Z
LDA
Exc [n] = drn(r)"HEG
xc (n(r))
HEG
"xc (n)
where is the exchange-correlation
energy of a homogeneous electron gas of density n
Generalized gradient approximations (GGA; semi-local functionals)

Z
GGA
Exc [n] = drn(r)"xc (n(r), n(r))

DFT in practice: The self-consistency loop
Initial guess (usually superposition of atomic densities for k=1)
n(k) (r)
k !k+1
Evaluate effective potential
ve↵ (r) = vext (r) + vH [n(k) (r)] + vxc [n(k) (r)]
Solve KS equations (for given potential)

✓ ◆
1 2
r + ve↵ [n(k) (r)] i (r) = ✏i i (r)
2
occ
X 2
Evaluate actual density n(r) = | i (r)|
i
Compute energy, Yes Consistent? No

(k)
forces, stresses … ||n (r) n(r)||2 <

Implementation aspects
Beyond DFT
DFT
✓ ◆
1 2
r + vext (r) + vHxc (r) i (r) = ✏i i (r)
2
In practice
• a lot of numerics related to basis sets, treatment of core/valence
electrons, exchange-correlation, solving differential equations,
finding eigen values etc.
• Actual production DFT codes contain
tens to hundreds of thousands of lines of code
• The one-electron orbitals (KS orbitals)

are solutions to the KS equation (one-particle equation!!)
✓ ◆
1 2
2
KS orbital
• It is tempting to treat these states as KS eigenenergy
proper electronic (quasi) particle states;
but beware, this are fictitious states
• Nonetheless band structures often useful;

although band gap underestimation is common

• Band gap underestimation
Solid State Physics (1970)
GW is a many body perturbation technique

G: Green’s function
W: Screened Coulomb interaction
• Band structures
silicon
• Dispersion usually very good

Beyond DFT
• DFT represents a very starting point for many-body perturbation theory
GW: LaBr3 Bethe-Salpeter equation (BSE)

Take away messages
1) n(r) ({r})
• Hohenberg-Kohn theorems
f=3 f=3N
1) All properties determined by density
2) A functional can be defined the minimum 2) vext (r) HK n0 (r)
of which yields the ground state
• Kohn-Sham equations n ({r i }) 0 ({r i })

– Replace fully interacting system
with set of fictitious effective
single-particle problems vKS (r) n0 (r)
Kohn-Sham
– The magic happens in the
exchange-correlation functional
– Can be solve iteratively i=1...N (r)
DFT yields total energies, forces, and electronic structure

à excellent starting point for many-body perturbation theory
techniques (GW, BSE, also TD-DFT)
Take away messages
Density functional theory (DFT)
• … yields total energies, forces, and electronic structure
and therefore allows computing e.g.,
– Structural relaxation and phase stability
– Energy differences (input for thermodynamics, kinetics …)
– Phonon dispersions (mechanical stability)
– Property prediction and screening
– Band structures (a bit more complicated, see above)
• … provides a reasonable balance between
computational efficiency and accuracy
(thousands of electrons, hundreds of atoms)
• … has limitations e.g., with respect to

– Band gaps and optical properties (excitonic effects)
– Strongly correlated systems

Lecture VIII DFT-3

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Lecture VIII DFT-3

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A

very short introduction to

FKA091 - Condensed matter physics

• What is density functional theory (DFT) good for?

• Kohn-Sham equations and the exchange-correlation functional

Erhart, FKA091 11/2016

Erhart, FKA091 11/2016

Balance between computational effort

Erhart, FKA091 11/2016

• Enables calculation of total energies and forces

Ĥ = T̂r + T̂R + V̂r + V̂r,R + V̂R

V̂mn depends on derivatives of electronic states

… and choose a representation (the so-called adiabatic representation),

Born-Oppenheimer approximation = neglect of cross terms

Erhart, FKA091 11/2016

1. The electron-structure problem: Regard the nuclei as fixed in space

The Hohenberg-Kohn theorems

Hohenberg and Kohn, 1964 (HK):

Ĥ = T̂r + V̂r + V̂r;R Reduction of dimensionality!

given an HK the ground state

a solution to the the ground state

Erhart, FKA091 11/2016

Similarly consider a second system of N particles 0

Then by the variational principle

Erhart, FKA091 11/2016

Adding the inequalities gives Z

n0 (r) ⌘ n(r) is excluded as this would result in 0<0

Thus any potential except

Erhart, FKA091 11/2016

Thus by means of minimization, the

Erhart, FKA091 11/2016

The universal functional contains the individual contributions of

Erhart, FKA091 11/2016

• The HK theorems can be generalized to include spin

• … reformulate the many-body problem in terms of the density

• The HK functional is a priori unknown!

• HK-DFT is in principle exact (no approximations) but impractical

Erhart, FKA091 11/2016

The Kohn-Sham equations

1998 (chemistry) Erhart, FKA091 11/2016

• Fock: does not satisfy anti-symmetry requirement (fermions)

D. R. Hartree Erhart, FKA091 11/2016

• In principle, the solution of the independent KS problem

n ({r i }) 0 ({r i }) i=1...N (r)

The auxiliary Hamiltonian contains the usual kinetic energy term

Erhart, FKA091 11/2016

N.B.: Here, we use atomic units. Erhart, FKA091 11/2016

The universal functional contains the individual contributions of

Erhart, FKA091 11/2016

Jones, Gunnasson (1989)

kinetic Coulombic exchange-correlation (XC)

XC is on an absolute scale a minor contribution to the total energy.

• The one-electron orbitals (KS orbitals)

• Nonetheless band structures often useful;

Erhart, FKA091 11/2016

Generalized gradient approximations (GGA; semi-local functionals)

Erhart, FKA091 11/2016

Solve KS equations (for given potential)

Compute energy, Yes Consistent? No

Erhart, FKA091 11/2016

• The one-electron orbitals (KS orbitals)

• Nonetheless band structures often useful;

Erhart, FKA091 11/2016

Solid State Physics (1970)