Metal-insulator transitions

What can we learn from electronic structure calculations?

Mike Towler
[email protected]
www.tcm.phy.cam.ac.uk/mdt26

Theory of Condensed Matter Group

Cavendish Laboratory
University of Cambridge
1

Metal-insulator transitions
What is an insulator?

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).
Band theory (one-electron wave functions)
Fermi level lies within a band gap rather than within a band.

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).
Band theory (one-electron wave functions)
Fermi level lies within a band gap rather than within a band.
Quantum Monte Carlo (many-electron wave functions)
Thought required.. [What about Kohn theory (1964) and modern
reinterpretations?]

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).
Band theory (one-electron wave functions)
Fermi level lies within a band gap rather than within a band.
Quantum Monte Carlo (many-electron wave functions)
Thought required.. [What about Kohn theory (1964) and modern
reinterpretations?]
Associated questions

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).
Band theory (one-electron wave functions)
Fermi level lies within a band gap rather than within a band.
Quantum Monte Carlo (many-electron wave functions)
Thought required.. [What about Kohn theory (1964) and modern
reinterpretations?]
Associated questions
What is meant by localized/delocalized electrons?

Metal-insulator transitions
What is an insulator?
Phenomenological
- Has vanishing electrical conductivity in a (weak) static electrical field
at 0K.
- Supports bulk macroscopic polarization (pure ground state property!).
Band theory (one-electron wave functions)
Fermi level lies within a band gap rather than within a band.
Quantum Monte Carlo (many-electron wave functions)
Thought required.. [What about Kohn theory (1964) and modern
reinterpretations?]
Associated questions
What is meant by localized/delocalized electrons?
What are strongly correlated electrons?
2

Connections

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calculations
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insulators)
True manybody
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wave functions.
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Metalinsulator
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transitions from the
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stronglycorrelated
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electrons community.
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Modern theory of
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polarization/localization
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(Resta
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techniques
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Mossbauer spectroscopy.. )
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Books
Metal-insulator Transitions 2nd edition, N. Mott (Taylor-Francis 1990)
The Mott Metal-insulator Transition : Models and Methods, F.Gebhard
(Springer, 1997)

Books
Metal-insulator Transitions 2nd edition, N. Mott (Taylor-Francis 1990)
The Mott Metal-insulator Transition : Models and Methods, F.Gebhard
(Springer, 1997)

GEBHARD IS GOSPEL

i.e. for the purposes of this talk, Gebhard is taken to represent the
strongly-correlated electron viewpoint, which we will attempt to
understand and interpret in terms more familiar to practitioners of
computational electronic structure theory.

Two fundamental requirements for electron transport

Two fundamental requirements for electron transport

Quantum-mechanical states for electron-hole excitations must be
available at energies immediately above the energy of the ground state
since the external field provides vanishingly small energy ( 0)
These excitations must describe delocalized charges that can contribute
to transport over the macroscopical sample size.

Scenarios for gap formation

Scenarios for gap formation

Quantum phase transition
Gap opens as a consequence of the competition between the carriers
kinetic and interaction energy.
= robust gap (doesnt disappear at high T )
Thermodynamic phase transitions
Gap opens as a consequence of the formation of long-range order
(symmetry breaking) at some finite temperature.
= soft gap (disappears at high T )

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction
Band insulators due to the electrons interaction with the periodic
potential of the ions.

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction
Band insulators due to the electrons interaction with the periodic
potential of the ions.
Peierls insulators due to the electrons interaction with static lattice
deformations.

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction
Band insulators due to the electrons interaction with the periodic
potential of the ions.
Peierls insulators due to the electrons interaction with static lattice
deformations.
Anderson insulators due to the presence of disorder.

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction
Band insulators due to the electrons interaction with the periodic
potential of the ions.
Peierls insulators due to the electrons interaction with static lattice
deformations.
Anderson insulators due to the presence of disorder.
Electron-electron interaction

Gebhard classification of insulators

Specify four basic classes of insulator, based on dominant interaction that
causes the insulating behaviour.
Electron-ion interaction
Band insulators due to the electrons interaction with the periodic
potential of the ions.
Peierls insulators due to the electrons interaction with static lattice
deformations.
Anderson insulators due to the presence of disorder.
Electron-electron interaction
Mott insulators due to the electrons interaction with each other.

Gebhard on band theory

For a band insulator the interaction between electrons and the periodic
ion potential gives rise to an energy gap between the lowest conduction
band and the highest valence band. Consequently there are no free carriers
for the transport of charge. A band insulator is possible only for an even
number of valence electrons per lattice unit cell.

Gebhard on band theory

For a band insulator the interaction between electrons and the periodic
ion potential gives rise to an energy gap between the lowest conduction
band and the highest valence band. Consequently there are no free carriers
for the transport of charge. A band insulator is possible only for an even
number of valence electrons per lattice unit cell.
Assumptions
electron-electron interaction neglected or treated within effective
single-electron approximation
For simplicity we neglect spin-orbit coupling. As a good approximation
each band is then two-fold spin degenerate i.e. each band may be occupied
with two electrons per k point.
= completely filled bands cannot contribute to transport (since for each
state with crystal momentum k the state with momentum k is also
occupied so that both contributions to transport cancel).

Band insulators
Impose periodic boundary conditions : the one-electron wave functions are
then Bloch functions.
Bloch functions obey BLOCHS THEOREM:
nk(r) = eikrunk(r) or (r + t) = (r)eikt

Count states in each energy range, and classify:

Increasing pressure (for example) will change shape of bands and may lead
to metal-insulator transitions of various sorts.
9

What is a Mott insulator?

Gebhard
For a Mott insulator the electron-electron interaction leads to the
occurence of local moments. The gap in the excitation spectrum for
charge excitations may arise from the long-range order of the pre-formed
moments (Mott-Heisenberg insulator) or by a quantum phase transition
induced by charge and/or spin correlations (Mott-Hubbard insulator)
Mott insulating behaviour is understood as a cooperative many-electron
phenomenon.. [It] cannot be understood within the framework of a
single-electron theory - many-body effects must be included.
..materials in which electron-electron interactions [are so] important
that a naive band structure approach will no longer be appropriate

What is a Mott insulator?

Gebhard
For a Mott insulator the electron-electron interaction leads to the
occurence of local moments. The gap in the excitation spectrum for
charge excitations may arise from the long-range order of the pre-formed
moments (Mott-Heisenberg insulator) or by a quantum phase transition
induced by charge and/or spin correlations (Mott-Hubbard insulator)
Mott insulating behaviour is understood as a cooperative many-electron
phenomenon.. [It] cannot be understood within the framework of a
single-electron theory - many-body effects must be included.
..materials in which electron-electron interactions [are so] important
that a naive band structure approach will no longer be appropriate
Mott
..a material that would be a metal if no moments were formed.
...depends on the existence of moments and not on whether or not they
are ordered

What is a Mott insulator?

Gebhard
For a Mott insulator the electron-electron interaction leads to the
occurence of local moments. The gap in the excitation spectrum for
charge excitations may arise from the long-range order of the pre-formed
moments (Mott-Heisenberg insulator) or by a quantum phase transition
induced by charge and/or spin correlations (Mott-Hubbard insulator)
Mott insulating behaviour is understood as a cooperative many-electron
phenomenon.. [It] cannot be understood within the framework of a
single-electron theory - many-body effects must be included.
..materials in which electron-electron interactions [are so] important
that a naive band structure approach will no longer be appropriate
Mott
..a material that would be a metal if no moments were formed.
...depends on the existence of moments and not on whether or not they
are ordered
Pasternak (an experimentalist)
In this [W > U ] regime, the d-electron correlation collapses, giving rise
to an insulator-metal transition concurrent with a magnetic moment
breakdown. This phenomenon is called the Mott transition.
10

Anderson insulators

11

Linear chain of hydrogen atoms

Consider a linear chain of hydrogen atoms with a lattice constant of 1

A.
This has one electron per atom in the conduction band and is therefore
metallic. Imagine we now dilate the lattice parameter of the crystal to 1
metre. We would agree that at some point in this dilation process the
crystal must become an insulator because certainly when the atoms are 1
metre apart they are not interacting. But band theory says that the crystal
remains a metal because at all dilations the energy difference between
occupied and unoccupied states remains vanishingly small. Now look at
this thought experiment from the other way. Why is the crystal with a
lattice parameter of 1 metre an insulator? Because to transfer an electron
from one atom to another we have to supply an ionization energy, I to
remove the electron and then we recover the electron affinity, A, when we
add the electron to the neutral H atom. The energy cost in this process is
U = I A. Band theory ignores terms such as these. [Suttons book]
Hubbard model
P
P
H = i,j tij ai aj + U i nini

12

DFT treatment of linear hydrogen chain

Examine linear chain of H atoms in band theory
Genuine 1-dimensional periodic boundary conditions
High quality local (Gaussian) basis set centred on the H atoms.
Properties of isolated H atom computed with this basis
Total energy (HF)
Virial coefficient
Hyperfine coupling constant

Calculated
-0.499993 Ha
1.00007
1419.3 MHz

Exact
-0.5 Ha
1
1420 MHz

13

Band theory of linear hydrogen chain

(DFT band calculations with LDA exchange-correlation functional)
1 atom per cell

Total energy (a.u.)

-0.46

-0.48

-0.5
Metallic at all dilations
-0.52

-0.54

-0.56

Lattice spacing ()

10

Band theory of linear hydrogen chain

(DFT band calculations with LDA exchange-correlation functional)
1 atom per cell

Total energy (a.u.)

-0.46

-0.48

-0.5
Metallic at all dilations
-0.52

-0.54

-0.56

10

Lattice spacing ()

DENSITY OF STATES (STATES/HARTREE/CELL)

200

a = 3
150

100

50

0
-0.4

-0.35

-0.3

-0.25

-0.2

-0.15

ENERGY (HARTREE)

-0.1

-0.05

14

Correlated electron systems

Strong Coulomb interactions : actually statement about pair correlation
function.

TRUE MANY-BODY EFFECTS HERE

correlated electron system - non-vanishing pair correlation function
between - and -electrons
strongly-correlated system - pair correlation functions for electrons of
same spin and electrons of opposite spin are comparable in size

Correlated electron systems

Strong Coulomb interactions : actually statement about pair correlation
function.

TRUE MANY-BODY EFFECTS HERE

correlated electron system - non-vanishing pair correlation function
between - and -electrons
strongly-correlated system - pair correlation functions for electrons of
same spin and electrons of opposite spin are comparable in size
So to describe strong-correlations just need to make the wave function
flexible enough for - and -electrons to avoid each other?

15

Spin polarization
Need single determinants of one-electron spin orbitals!
Restricted form All spin orbitals are pure space-spin products of the form
n or n and are occupied singly or in pairs with a common orbital
factor n.
Unrestricted form Spin orbitals no longer occupied in pairs but still pure
space-spin products n or n. However, now have different spatial
factors n and n for different spins.
General unrestricted form No longer restrict to simple product form.
Each spin orbital now a 2-component complex spinor orbital:

1 =

and

2
1
2
1
2 . Non-collinear spins.
Pretty pictures of non-collinear spin states

16

Spin-unrestricted band treatment of

linear hydrogen chain
(LSDA functional)
-0.46
1 atom per cell

-0.47
-0.48

Total energy (a.u.)

-0.49
-0.5

ferromagnetic
spin-unpolarized

-0.51
-0.52
-0.53
-0.54
-0.55
METAL

-0.56
0

INSULATOR

Lattice spacing ()

17

Band structure of linear hydrogen chain

Hydrogen linear chain (a=3 )
Band structure
0.05

Energy (au)

-0.05

-0.1

-0.15

-0.2

-0.25

-/2a

/2a

18

Spin-unrestricted band treatment of

linear hydrogen chain
Hydrogen linear chain
Density of states
40
20

40
6

20

40
3

20

-20

-20

-20

-40
-0.4 -0.3 -0.2 -0.1
40
20

2.1

-40
-0.4 -0.3 -0.2 -0.1
40
20

2.05

-40
-0.4 -0.3 -0.2 -0.1
40
20

-20

-20

-20

-40
-0.4 -0.3 -0.2 -0.1
40
20

2.0

-40
-0.4 -0.3 -0.2 -0.1
40
20

1.9

20

-20

-20

-20

-40
-0.4 -0.3 -0.2 -0.1

2.02

-40
-0.4 -0.3 -0.2 -0.1
40

-40
-0.4 -0.3 -0.2 -0.1

2.5

1.5

-40
-0.4 -0.3 -0.2 -0.1

ENERGY (HARTREE)

19

Spin-unrestricted band treatment of

linear hydrogen chain
Total energy of a linear chain of hydrogen atoms
(spin-unrestricted DFT band calculations with LSDA functional)
2 atoms per cell

Total energy (a.u.)

-0.48

-0.5
ferromagnetic
antiferromagnetic
-0.52

-0.54
METAL
-0.56

INSULATOR

Lattice spacing ()

20

Hubbard bands
[Mott book]

Let i be the many electron wave function with an extra electron on atom
i. A state in which the electron moves with wave number k can be
described by the many-electron wave function:
X
eikai i
i

These states form a band of energies - this is called the upper Hubbard
band - (a). Similarly, the lower Hubbard band - (b) - represents a band of
states in which a hole can move. Metal-insulator transition occurs when
these bands overlap.
21

N+1/N-1 system

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U=

U (as above)
U (Band gap)

LSDA (eV)
11.44
5.30

UHF (eV)
13.03
11.99

B3LYP (eV)
12.01
8.56

Should be around 13 eV.

22

N+1 system
Total energy of N+1 hydrogen chain
10 atoms and 11 electrons per cell (LSDA)
(ferro)magnetic insulator
-0.48

Total energy per atom (a.u.)

1
8

10

-0.5

(ferro)magnetic metal

-0.52

-0.54

Non-magnetic metal

-0.56
0

10

Lattice spacing ()

23

Effect of extra electron on the density of states

DENSITY OF STATES (STATES/HARTREE/CELL)

1000

up spin

-1000

N case
a = 8.5
down spin
-0.55 -0.5 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05
ENERGY (HARTREE)

0.05

0.1

Effect of extra electron on the density of states

DENSITY OF STATES (STATES/HARTREE/CELL)

1000

up spin

N case
a = 8.5
down spin

-1000

-0.55 -0.5 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05

0.05

0.1

ENERGY (HARTREE)

DENSITY OF STATES (STATES/HARTREE/CELL)

1000

up spin

-1000

N+1 case
a = 8.5
down spin
-0.55 -0.5 -0.45 -0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05
ENERGY (HARTREE)

0.05

0.1

24

Localization
Insulating state of matter is characterized by gap to low-lying excitations,
but also by qualitative features of the ground state - which sustains
macroscopic polarization and is localized.
Kohn 1964
Localization is a property of the many-electron wave function: insulating
behaviour arises whenever the ground state wave function of an extended
system breaks up into a sum of functions M which are localized in
essentially disconnected regions RM of configuration space i.e.
(x1, . . . , xN ) =

+
P

M (x1, . . . , xN )

M =

where for a large supercell M and M 0 have an exponentially small

overlap for M 0 6= M . Under such a hypothesis, Kohn proved that the dc
conductivity vanishes.
Hence, electronic localization in insulators does not occur in real space
(charge density) but in configuration space (wave function).

25

Many-body phase operators

Both macroscopic polarization and electron localization are expectation
()
values of many-body phase operators zN , where
(x)
zN

= h|e

i 2
L

These quantities are zero for metals!

PN

i=1 xi

|i

Many-body phase operators

Both macroscopic polarization and electron localization are expectation
()
values of many-body phase operators zN , where
(x)
zN

= h|e

i 2
L

PN

i=1 xi

|i

These quantities are zero for metals!

Ground state expectation value of the position operator in periodic
boundary conditions

hXi =

L
Im ln zN
2

Many-body phase operators

Both macroscopic polarization and electron localization are expectation
()
values of many-body phase operators zN , where
(x)
zN

= h|e

i 2
L

PN

i=1 xi

|i

These quantities are zero for metals!

Ground state expectation value of the position operator in periodic
boundary conditions

hXi =

()

L
Im ln zN
2

Phase of zN used to define the macroscopic polarization of an insulator.

Many-body phase operators

Both macroscopic polarization and electron localization are expectation
()
values of many-body phase operators zN , where
(x)
zN

= h|e

i 2
L

PN

i=1 xi

|i

These quantities are zero for metals!

Ground state expectation value of the position operator in periodic
boundary conditions

hXi =

L
Im ln zN
2

()

Phase of zN used to define the macroscopic polarization of an insulator.

()

Modulus of zN used to define the localization tensor hrr i (finite in

insulators, diverges in metals).
26

Interesting connections
One-particle density matrix

hrr i =

1
2nb

Z
dr
cell

dr0(r r0)(r r0) |P (r, r0)|2

allspace

which is the second moment of the (squared) density matrix in the

coordinate r r0.

Interesting connections
One-particle density matrix

hrr i =

1
2nb

Z
dr
cell

dr0(r r0)(r r0) |P (r, r0)|2

allspace

which is the second moment of the (squared) density matrix in the

coordinate r r0.
Conductivity
Vc
h
hrr i =
2e2nb

Z
0

d
Re ()

where is the conductivity tensor. LHS property of ground state, RHS

measurable property related to electronic excitations = localization
tensor is a measurable property.

Interesting connections
One-particle density matrix

hrr i =

1
2nb

Z
dr
cell

dr0(r r0)(r r0) |P (r, r0)|2

allspace

which is the second moment of the (squared) density matrix in the

coordinate r r0.
Conductivity
Vc
h
hrr i =
2e2nb

Z
0

d
Re ()

where is the conductivity tensor. LHS property of ground state, RHS

measurable property related to electronic excitations = localization
tensor is a measurable property.
Nearsightedness
is the fact that the density matrix P (r r0) is short range in the variable
r r0. The localization tensor is a measure of this.
27

Crystal field splitting of d orbitals

(octahedral coordination)

28

Electronic states in NiO

Interactions:
Parameterize on-site interactions in terms of U and U 0 (Coulomb
interactions between electrons in same (U ) or different (U 0) d orbitals) and
J (exchange interaction between same spin electrons). Augment with
CF i.e. crystal-field splitting energy due to neighbours.
-spin
-spin
-spin
-spin

On a Ni site in NiO:
eg electron feels: 7U 0 4J + CF
t2g electron feels: U + 6U 0 4J
eg electron feels: U + 7U 0 3J + CF
t2g electron feels: U + 6U 0 2J

Expt: U=5.8eV, J=0.67eV, U=4.5eV, CF =1.1eV

up spin

down spin

U3J+ CF

eg

t2g
t2g
2J
eg

2J

CF

29

eg
eg

t2g

t2g
2J
CF
0.5

U3J+ CF

0.25

0.25

0.5
ENERGY relative to highest occupied level (au)

downspin

upspin

0.75

total oxygen

Ni t2g

Ni eg

down spin

DENSITY OF STATES

up spin

Antiferromagnetic (AF2)

Compare model with NiO UHF DOS

2J

30

UHF : effect of magnetic ordering

Antiferromagnetic (AF2)

Ni eg
Ni t2g

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

0.75

ENERGY relative to highest occupied level (au)

Ferromagnetic

Ni eg
Ni t2g

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

ENERGY relative to highest occupied level (au)

0.75

31

UHF vs. LDA

Antiferromagnetic (AF2)

Ni eg
Ni t2g

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

0.75

ENERGY relative to highest occupied level (au)

LSDA

Ni t2g

AF2

Ni eg

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

ENERGY relative to highest occupied level (au)

0.75

32

UHF vs. GGA

LSDA

Ni t2g

AF2

Ni eg

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

0.75

ENERGY relative to highest occupied level (au)

GGA

Ni t2g

AF2

Ni eg

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

ENERGY relative to highest occupied level (au)

0.75

33

UHF vs. B3LYP

Antiferromagnetic (AF2)

Ni eg
Ni t2g

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

0.75

ENERGY relative to highest occupied level (au)

B3LYP

Ni t2g

AF2

Ni eg

DENSITY OF STATES

total oxygen
upspin

downspin

0.5

0.25

0.25

0.5

ENERGY relative to highest occupied level (au)

0.75

34

Band gaps with the B3LYP functional

Material
Si
Diamond
GaAs
ZnO
Al2O3
Cr2O3
MgO
MnO
NiO
TiO2
FeS2
ZnS

Expt. (eV)
3.5
5.5
1.4
3.4
9.0
3.3
7.8
3.6
4.3
3.0
1.0
3.7

B3LYP (eV)
3.8
5.8
1.5
3.2
8.5
3.4
7.3
3.8
3.9
3.4
2.0
3.5

35

Orbital interactions
How do orbitals interact in the Hartree-Fock approximation?
P
+ P haa k bbi hab k bai
E0 = a ha|h|ai
ab
Coulomb interaction
haa k bbi =

dr1dr2 |a(r1)|

2 1
r12

|b(r2)|

exchange interaction
hab k bai =

dr1dr2 a(r1)b (r1) r112 b(r2)a(r2)

36

Self-interaction - Hartree-Fock case

Label orbitals occupied (a, b, . . .) or virtual (i, j, . . .). What is the
expression for the orbital energy?

Self-interaction - Hartree-Fock case

Label orbitals occupied (a, b, . . .) or virtual (i, j, . . .). What is the
expression for the orbital energy?
Occupied
P
N
ai +
a = ha|h|
b=1 (ha a || b b i ha b || b a i)

Self-interaction - Hartree-Fock case

Label orbitals occupied (a, b, . . .) or virtual (i, j, . . .). What is the
expression for the orbital energy?
Occupied
P
N
ai +
a = ha|h|
b=1 (ha a || b b i ha b || b a i)
ii +
i = hi|h|

Virtual
b=1 (hi i k b b i hi b k b i i)

PN

Self-interaction - Hartree-Fock case

Label orbitals occupied (a, b, . . .) or virtual (i, j, . . .). What is the
expression for the orbital energy?
Occupied
P
N
ai +
a = ha|h|
b=1 (ha a || b b i ha b || b a i)
ii +
i = hi|h|

Virtual
b=1 (hi i k b b i hi b k b i i)

PN

Sum over b is over occupied orbitals only. Therefore for the first
expression only, one of the terms will cancel when b=a:
haa k aai haa k aai = 0

Self-interaction - Hartree-Fock case

Label orbitals occupied (a, b, . . .) or virtual (i, j, . . .). What is the
expression for the orbital energy?
Occupied
P
N
ai +
a = ha|h|
b=1 (ha a || b b i ha b || b a i)
ii +
i = hi|h|

Virtual
b=1 (hi i k b b i hi b k b i i)

PN

Sum over b is over occupied orbitals only. Therefore for the first
expression only, one of the terms will cancel when b=a:
haa k aai haa k aai = 0
Therefore in the Hartree-Fock approximation an electron does not feel its
own field, since the self-interaction is cancelled by an equivalent term in
the exchange energy.

37

Self-interaction in local density approximation to DFT

LSDA exchange energy
Z
Ex = dr x [(r), (r)]

Self-interaction in local density approximation to DFT

LSDA exchange energy
Z
Ex = dr x [(r), (r)]

Mean-field contains all the electrons

Self-interaction in local density approximation to DFT

LSDA exchange energy
Z
Ex = dr x [(r), (r)]

Mean-field contains all the electrons

Implications:

Self-interaction in local density approximation to DFT

LSDA exchange energy
Z
Ex = dr x [(r), (r)]

Mean-field contains all the electrons

Implications:
U (interpreted as the self-exchange term) equals J (the different
orbital exchange term).
But U and J differ by an order of magnitude in NiO. LSDA effectively
averages these quantities.
Therefore additional potential U felt by unoccupied orbitals disappears,
and instead all the states are shoved up in energy by something like the
average of U and J.
Local density theory lumps all these exchange interactions together and
thus dilutes the effect of self-exchange and underestimates the driving force
for the formation of a correlated state. This is the root of the difficulty of
contemporary calculations in describing strongly-correlated systems.
38

What to do about it
Problem:
The effect of self-interaction and the use of simple local exchange
functionals (inherent in LSDA and all GGA treatments) will often lead to
the wrong ground state in magnetic insulators and other strongly
correlated materials.

What to do about it
Problem:
The effect of self-interaction and the use of simple local exchange
functionals (inherent in LSDA and all GGA treatments) will often lead to
the wrong ground state in magnetic insulators and other strongly
correlated materials.
Possible ways to improve this:

What to do about it
Problem:
The effect of self-interaction and the use of simple local exchange
functionals (inherent in LSDA and all GGA treatments) will often lead to
the wrong ground state in magnetic insulators and other strongly
correlated materials.
Possible ways to improve this:
Use corrections to LDA treatment (LDA+U, SIC-LDA).
Use unrestricted Hartree-Fock calculations.
Use hybrid functionals in DFT containing some fraction of the
non-local HF exchange (e.g. B3LYP)
Use exact-exchange DFT treatments currently being developed.
Use the result of any of the above as a trial wave function for quantum
Monte Carlo (which is self-interaction free).

39

Results for some simple properties of NiO

UHF
LSDA
GGA
B3LYP
DMC(UHF)
DMC(B3LYP)
Exp.

a (
A)
4.26
4.09
4.22
4.22
(4.16ish?)

EC (eV)
6.2
10.96
8.35
7.8
9.44(13)
9.19(14)
9.45(?)

4.165

Eg (eV)
14.2
0
0
3.9
4.3(2)
4.04.3

Lattice constant, a, cohesive energy, EC , and band gap, Eg , of NiO.

0.02
0.018

DMC
HF
LDA

0.016

Change in energy (Ha)

0.014

DMC calculations still running!

0.012
0.01
0.008

Expt = 4.165

0.006
0.004
0.002
0
-0.002
3.9

3.95

4.05

4.1

4.15

4.2

4.25

Lattice constant ()

4.3

4.35

4.4

4.45

4.5

40

Real Mott transitions

Experimental techniques
very high pressure diamond anvil cells ( Mbar range)
Mossbauer spectroscopy - probes spins through hyperfine fields - only
high pressure method for probing sensitive magnetic phenomena like
HS LS transitions etc..
synchrotron X-ray diffraction
resistance measurements
Examples NiI2, CoI2, Fe2O3, FeO

41

Things to do (maybe)
Research
Implement calculation of many-body phase operators in CASINO QMC
code (easy!).
Check if results of above make sense in very simple systems (like
hydrogen chain!) then repeat in simple materials like aluminium and
carbon.
Check out the Mott transitions in e.g. NiI2, CoI2, Fe2O3, etc. HS LS
transition in FeO with both DFT and QMC calculations.
Things to think about
The mathematics of Berry phases and many-body phase operators in
periodic boundary conditions..
Clarify the connections between localization tensors, maximally localized
Wannier functions, conductivity, nearsightedness, density matrices, Boys
localization, Kohn theory, polarization etc..

42

Conclusions

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

QUANTUM MONTE CARLO

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

QUANTUM MONTE CARLO

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

QUANTUM MONTE CARLO

VERY ACCURATE NUMBERS AND LOCALIZATION PROPERTIES!

Conclusions
To a first approximation, strong correlations can be described by simply
allowing spin polarization i.e. allowing the density of up-spin electrons to
differ from the density of down-spin electrons (controversial!).
If you allow the latter, many features of the Mott transition appear to
be recovered from band overlap transitions within spin-polarized band
theory.
Clearly can calculate trial wave functions for QMC off the back of this,
and can calculate the localization tensor? What else do we need to
describe a Mott transition?
REASONABLE GUESS AT WAVE FUNCTION

QUANTUM MONTE CARLO

VERY ACCURATE NUMBERS AND LOCALIZATION PROPERTIES!

Hurray!

43