First principles electronic

structure: density functional

theory
 Electronic Schroedinger equation

Atomic units, classical nuclei, Born-

Oppenheimer approximation.

Describes 99% of condensed matter, materials

physics, chemistry, biology, psychology,
sociology, ....

3 basic parameters: electronic mass, proton

mass, electric charge 2
• Prediction: in principle, just need to know what
atoms are, can predict all properties of
quantum system to very high accuracy

No parameters, no ‘garbage in,

garbage out’
3
 Solving the Schroedinger Equation
• For example, consider that we have n electrons populating a 3D space. Let’s divide
3D space into NxNxN=2x2x2 grid points. To reconstruct Ψ, how many points must
we keep track of?

Y =Y ( r1,..., rn ) # of points =N 3n

n=# Ψ (N3n) ρ (N3)

electrons
N 1 8 8
10 109 8
N  N  
100 1090 8
1000 10900 8

4
Two solution philosophies (approximate)
Variational wave
Density functional
functions (CI, CC,
theory
VMC, DMC)
Many-body wave
Basic object Density
function

Basic equation E=F[p] Hψ=Eψ

Efficient
Density is only a 3D
Efficiency strategy parameterization of the
function
wave function
Don’t know the Run out of computer
Accuracy limitation
functional time to add parameters

Argue functional is
Variational theorem:
Argument for accuracy accurate, compare to
lower energy is closer
experiment
5
 Density functional theory
• Hohenberg and Kohn (Phys. Rev. 1964)
introduced two theorems:
– Electron density <-> the external potential +
constant
– Total energy of any density is an upper bound to
the ground state energy, if we know the
functional

– But mapping is unknown

Very clear and detailed proofs of these theorems can be found in

“Electronic Structure,” Richard M. Martin (Cambridge University Press
2004 ,ISBN 0 521 78285 6).
 First theorem
• For each external potential, there is a unique
ground state electronic density
• proof outline:
1. Suppose there are two different potentials
2. Suppose they have the same ground state density
3. Show that this leads to an inconsistency
 Hohenberg-Kohn I
- The external
potential corresponds
to a unique ground
state electron density.
- A given ground state
electron density
corresponds to a
unique external
potential
- In particular, there is
a one to one
correspondence
between the external
potential and the
 Second theorem
– Variational principle with respect to the density
– instead of finding an unknown function of 1023
variables, we need only find an unknown
function of 3, the charge density.
– incredible simplification:

Etot [ n( r) ] =T [ n( r) ] + Eint [ n( r) ] + òdrVext ( r) n( r) + Eion- ion

– Still need to find the functional!

 What might F[ρr)] look like?
From simple inspection:

E = òY (Vext + T + Vint )Y d r
* 3n

UNIVERSAL
!

 
E [ r (r)] = òVext (r)r(r)dr + F [ r(r)]

Naively, we might expect the functional to contain terms that

resemble the kinetic energy of the electrons and the coulomb
 
interaction of the electrons
 Ingredients of Density Functional Theory
• Ingredients:
– Note that what differs from one electronic system to another is the
external potential of the ions
– Hohenberg-Kohn I: one to one correpondence between the external
potential and a ground state density
– Hohenberg-Kohn II: Existence of a universal functional such that the
ground state energy is minimized at the true ground state density

E =min {
r
òV ext (r) r (r)dr + F [ r(r)] }

UNIVERSAL
!
• The universality is important. This functional is exactly the same for any
electron problem. If I evaluate F for a given trial orbital, it will always be the
  same for that orbital - regardless of the system of particles.
– Kohn-Sham: a way to approximate the functional F
 Euler-Lagrange System
The Hohenberg-Kohn theorems give us a variational
statement about the ground state density:

d dF
E - m òr( r) dr Þ
( ) + Vext =m
dr dr
“the exact density makes the functional
derivative of F exactly equal to the negative of
the external potential (to within a constant)”

 
If we knew how to evaluate F, we could solve all
Coulombic problems exactly.
However, we do not know how to do this. We must,
instead, approximate this functional. This is where
Kohn-Sham comes in.
 Kohn-Sham Approach
Kohn and Sham said:

F [ r (r)] =E KE [ r(r)] + E H [ r(r)] + E XC [ r(r)]

Separate kinetic energy coulomb energy, and

other
 
Kinetic energy of the system of non-interacting
electrons at the same density.

Coulomb is the electrostatic term (Hartree)

Exchange-correlation is everything else

 Kohn-Sham Approach
The next step to solving for the energy is to introduce a set of
one-electron orthonormal orbitals.
N
r (r) =å j i (r)
2

i=1

Now the variational condition can be applied, and one obtains the
one-electron Kohn-Sham equations.
 

Where VXC is the exchange correlation functional, related to the

xc energy as:
ædE XC [ r (r)] ö
VXC [ r] =ç ÷
è dr (r) ø
 The Exchange-Correlation Functional
The exchange-correlation functional is clearly the key to success
of DFT.

One of the great appealing aspects of DFT is that even relatively

simple approximations to VXC can give quite accurate results.

The local density approximation (LDA) is by far the simplest and

used to be the most widely used functional.

Approximate as the xc energy of homogeneous electron gas

Ceperley and Alder* performed accurate quantum Monte Carlo

calculations for the electron gas

Fit energies(e.g., Perdew-Zunger) to get f(p)

 Solving the Kohn-Sham System

To solve the Kohn-Sham equations, a number of different

methods exist.

Basis set expansion of the orbitals

-Localized orbitals : molecules, etc
-Plane waves: solids, metals, liquids

Meaning of the orbitals:

-Kohn-Sham: In principle meaningless, only representation of
the density
-Hartree-Fock: Electron distributions in the non-interacting
approximation

There is some ad-hoc justification for using K-S orbitals as

approximate quasiparticle distributions, but it’s qualitative at
best (see Fermi liquid theory).
 self-consistent approach
• like Hartree, LDA-DFT
equations must be solved self-
consistently
• great effort to develop
efficient and scalable
algorithms
– remarkably successful
– widely available
• can download computer
codes that perform these
calculations
 Local Density Approximation
In the original Kohn-Sham paper, the authors themselves cast
doubt on its accuracy for many properties. “We do not expect
an accurate description of chemical bonding.”

And yet, not until at least 10 years later (the 70’s), time and
time again it was shown that LDA provided remarkably
accurate results.

LDA was shown to give excellent agreement with experiment

for, e.g., lattice constants, bulk moduli, vibrational spectra,
structure factors, and much more.

One of the reasons for its huge success is that, in the end, only
a very
For small part
example, hereofare
thevarious
energy is approximated.
energy contributions for a Mn atom:
• Hartree (ECV, EVV)
• Kinetic (T0,V)
• Exchange (EX)
• Correlation energy is about EC ~
0.1EX
 Local Density Approximation
LDA also works well because errors in the approximation of
exchange and correlation tend to cancel.

For example, in a typical LDA atom, there’s a ~10%

underestimate in the exchange energy.

This error in exchange is compensated by a ~100-200%

overestimate of the correlation energy.
 Local Density Approximation
In theory, the LDA method should work best for systems with
slowly varying densities (i.e., as close to a homogeneous
electron gas as possible).

However, it is interesting that even for many systems where

the density varies considerably, the LDA approach performs
well!
Slow varying Faster varying
 Good & Bad - Local Density Approximation
Total energies
• Ground state densities well-represented
Cohesive energies are pretty
good; LDA tends to overbind a
system (whereas HF tends to
underbind)
Bond lengths are good, tend to
be underestimated by 1-2%
Good for geometries, vibrations,
Structures of highly correlated
systems (transition metals,
FeO, NiO, predicts the non-
magnetic phase of iron to be
ground state)
Doesn’t describe weak
interactions well.
Makes hydrogen bonds stronger
than they should be.
Band gaps (shape and position
is pretty good, but will
underestimate gaps by roughly
a factor of two; will predict
metallic structure for some
semiconductors)
 Local Density Approximation
One place where LDA performs poorly is in the calculation of
excited states.
 Beyond LDA
Description

LDA Value of the density

GGA (PBE, BLYP, PW91) Dependence on gradients

meta-GGA (TPSS) Laplacian

Ad-hoc correction for localized

DFT+U
orbitals

Hartree-Fock overestimates gaps. Mix

Hybrid DFT (B3LYP, HSE)
in ~20% of HF, get gaps about right.

29
• There are many different density functionals
• Each works best in different situations
• Difficult to know if it worked for the right
reasons

• Practically, very good accuracy/computational

cost

30