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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
Erhart, FKA091 11/2016
Some possible applications of DFT
Structure prediction and phase stability: Platinum series nitrides

Electronic structure
High pressure Low pressure
(single bonded nitrogen) (triple bonded nitrogen)
Erhart, FKA091 11/2016
Some possible applications of DFT
Defects: Thermodynamics, kinetics, electronic properties
Energetics – Which defects and how many

Vacancy level

Electronic structure
Total energies and forces à optical properties
Erhart, FKA091 11/2016
Some possible applications of DFT
Property prediction and screening: Substituted norbornadienes

donor

acceptor

Substitutions affect
position of absorption band
à can be tuned to solar spectrum
HOMO LUMO

Erhart, FKA091 11/2016


Some possible applications of DFT
Property prediction and screening: Substituted norbornadienes

Balance between computational effort


and accuracy/predictivness

Erhart, FKA091 11/2016


Some possible applications of DFT

• 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
Erhart, FKA091 11/2016
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
Erhart, FKA091 11/2016
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)
Erhart, FKA091 11/2016
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
Erhart, FKA091 11/2016
Born-Oppenheimer approximation
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

Erhart, FKA091 11/2016


Born-Oppenheimer approximation
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
Erhart, FKA091 11/2016
FKA091: Density functional theory

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
Erhart, FKA091 11/2016
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.

Erhart, FKA091 11/2016


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)

Erhart, FKA091 11/2016


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.

Erhart, FKA091 11/2016


Hohenberg-Kohn theorem #2
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

Erhart, FKA091 11/2016


Hohenberg-Kohn theorem #2
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 |

Erhart, FKA091 11/2016


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

Erhart, FKA091 11/2016


FKA091: Density functional theory

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

Erhart, FKA091 11/2016


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


Hohenberg-Kohn theorem #2
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 |

Erhart, FKA091 11/2016


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).
Erhart, FKA091 11/2016
Kohn-Sham one-electron orbitals

• The one-electron orbitals (KS orbitals)


are solutions to the KS equation (one-particle equation!!)
✓ ◆
1 2
r + vext (r) + vH (r) + vxc (r) i (r) = ✏i i (r)
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

Erhart, FKA091 11/2016


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))

Erhart, FKA091 11/2016


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 <

Erhart, FKA091 11/2016


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
Kohn-Sham one-electron orbitals

• The one-electron orbitals (KS orbitals)


are solutions to the KS equation (one-particle equation!!)
✓ ◆
1 2
r + vext (r) + vH (r) + vxc (r) i (r) = ✏i i (r)
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

Erhart, FKA091 11/2016


Kohn-Sham one-electron orbitals
• Band gap underestimation

Solid State Physics (1970)

GW is a many body perturbation technique


G: Green’s function
W: Screened Coulomb interaction
Erhart, FKA091 11/2016
Kohn-Sham one-electron orbitals
• Band structures

silicon

• Dispersion usually very good

Erhart, FKA091 11/2016


Beyond DFT

• DFT represents a very starting point for many-body perturbation theory

GW: LaBr3 Bethe-Salpeter equation (BSE)

Erhart, FKA091 11/2016


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)
Erhart, FKA091 11/2016
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
Erhart, FKA091 11/2016