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Bloch Bloch s theorem s theorem The The eigenstates eigenstates of such a one of such a one - - electron Hamiltonian can be written as electron Hamiltonian can be written as lattice Bravais a in all for ) ( ) ( where ), ( 2 2 2 R r U R r U r U m H General properties for a singe General properties for a singe - - electron Hamiltonian electron Hamiltonian ) ( ) ( r u e r k n r k i k n where where ) ( ) ( r u R r u k n k n

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Page 1: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

BlochBloch’’s theorems theorem

The The eigenstateseigenstates of such a oneof such a one--electron Hamiltonian can be written aselectron Hamiltonian can be written as

lattice Bravais ain allfor )()( where),(2

22

RrURrUrUm

H

General properties for a singeGeneral properties for a singe--electron Hamiltonianelectron Hamiltonian

)()( ruer knrki

kn

wherewhere

)()( ruRru knkn

Page 2: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Another statement of BlochAnother statement of Bloch’’s theorems theorem

The The eigenstateseigenstates of the Hamiltonian can be chosen to satisfy thatof the Hamiltonian can be chosen to satisfy that

)()( reRr Rki

Page 3: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Proof of BlochProof of Bloch’’s theorem:s theorem:

Defining a lattice translation operatorDefining a lattice translation operator RT

)()( RrfrfTR

Lattice translational symmetryLattice translational symmetry

RR HTRrrHRrRrHHT )()()()(

RR HTHT

On the other handOn the other hand

''' RRRRRR TTTTT

Page 4: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Now we will find the eigenvaluesNow we will find the eigenvalues )(Rc

)'(

)'()()'(

''

'

RRcTTT

RcRcTRcTT

RRRR

RRR

)'()()'( RcRcRRc

332211 anananR LetLet

321 )()()()( 321nnn acacacRc

RT Each is associated with a good quantum number, Each is associated with a good quantum number, consequencelyconsequencely, the , the eigenstateseigenstates can be chosen as can be chosen as eigenstateseigenstates of simultaneously. of simultaneously. RT

)(RcTEH

R

where are three primitive vectors for the Bravais latticewhere are three primitive vectors for the Bravais lattice..ia

Page 5: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

We can always write the asWe can always write the as)( iac

ixii eac 2)(

IntroducingIntroducing332211 bxbxbxk

where are the reciprocal lattice vectors satisfying where are the reciprocal lattice vectors satisfying ,,ib

ijji ab 2

we find thatwe find thatRkieRc)(

So thatSo that

)()( reRreT RkiRkiR

Page 6: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

BornBorn--von Karman boundary conditionvon Karman boundary condition

)()( raNr ii

integral ,

11 2

ii

ii

xNiakiN

mNmx

ee iiii

The general form of allowed Bloch wave vectorThe general form of allowed Bloch wave vector

integral ,3

1i

ii

i

i mbNmk

Volume occupied by per allowed wave vector in kVolume occupied by per allowed wave vector in k--spacespace

V

bbbNN

bNb

Nbk

3

3213

3

2

2

1

1 )2(1

Page 7: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

rqi

qqecr

)(

rKi

KKeUrU

)(

cell

rKiK rUerd

vU )(1

Another proof of BlochAnother proof of Bloch’’s theorems theorem

We can expand any function satisfying periodic boundary conditioWe can expand any function satisfying periodic boundary condition as follows, n as follows,

On the other hand, the periodic potential can be expanded asOn the other hand, the periodic potential can be expanded as

where the Fourier coefficients read where the Fourier coefficients read

Then we can study the SchrThen we can study the Schröödinger equation in dinger equation in kk-- space.space.

vector in reciprocal lattice

Page 8: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

rqiq

q

ecmq

mmp

222

22222

rqiKq

qKK

rqKiq

qKK

rqi

qq

rKi

KK

ecUecU

eceUU

''

',

)(

,

02 '

''

22

q KKqKq

rqi cUcEmqe

Kinetic partKinetic part

The term in potential energyThe term in potential energy

SchrSchröödinger equation in dinger equation in kk-- space.space.

Page 9: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

02 '

''

22

KKqKq cUcE

mq

KKKKkq '',

02

)('

''

22

K

KkKKKk cUcEm

Kk

SchrSchröödinger equation in dinger equation in kk-- space.space.

For any fix in the first Brillouin zone, it only couples to ,Then the wave function will be of the form

k

,',, KkKkk

)()( )( rueeceecr rkirKi

KKk

rkirKki

KKkk

rKi

KKk ecru

)(where satisfies )()( ruRru

Page 10: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

General remarks on BlochGeneral remarks on Bloch’’s theorems theorem

Wave vector , crystal momentum , and electron momentumWave vector , crystal momentum , and electron momentum

Equivalence between different wave vectorsEquivalence between different wave vectors

Band indexBand index

For a given , we expect to find infinite family of solutions For a given , we expect to find infinite family of solutions with discretely spaced with discretely spaced energy eigenvalues, which we label with the band index energy eigenvalues, which we label with the band index nn..

Band structure: Band structure: Periodic functions of in the reciprocal spacePeriodic functions of in the reciprocal space

CollisionlessCollisionless electron movement in a perfect crystalelectron movement in a perfect crystal

k

k

i

p

)())(( rui

ekrueii

p knrki

knknrki

knkn

not a momentum eigenstate,broken continuous symmetry

k

k

knKknknKkn EErr

,,,, ),()(

)(1)( kEkv nkn

It contradicts Drude’s ansatz

)()()()()(

)()(,'by Replace

')(

''

'

ruRrueRrurueru

rueerueKkkk

knknRrKi

knknrKi

kn

knrKirki

knrki

Page 11: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Electrons in a weak periodic Electrons in a weak periodic potentialpotential

•• Perturbation theory:Perturbation theory:•• Applicability: Applicability:

–– Metals in groups, I, II, III and IV, Metals in groups, I, II, III and IV, ss and and pp electronselectrons–– Pauli exclusion, conduction electronPauli exclusion, conduction electron--ion separation is not ion separation is not

very small, where core electrons have occupied the very small, where core electrons have occupied the immediate neighborhood of the ions.immediate neighborhood of the ions.

–– Screening effect will reduce the total effective potential.Screening effect will reduce the total effective potential.

Page 12: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Generic perturbation approachGeneric perturbation approach

,02

)('

''

22

K

KkKKKk cUcEm

Kk

.)( )( rKki

KKkk ecr

We begin with SchrWe begin with Schröödinger equation in periodic potential in kdinger equation in periodic potential in k--space space

with Bloch wave function with Bloch wave function

For real potential, we haveFor real potential, we have

,)( *KK UU

cell

rUrdv

U 0)(10

and can choose

by shifting the energy zero.

Page 13: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Free electronFree electron

,02

)(022

Kkk cE

mKkU

Introducing Introducing nonperturbativenonperturbative energyenergymqEq 2

220

rKkikKk eEE

)(0 ,

Page 14: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Issue: Issue: For a given there may be several reciprocal lattice vectorFor a given there may be several reciprocal lattice vectors s satisfyingsatisfying

k

,,,1 mKK

001 mKkKk EE

Case 1: Fix and consider a particular reciprocal lattice veCase 1: Fix and consider a particular reciprocal lattice vector such that ctor such that

the free electron energy is far away from the values the free electron energy is far away from the values of (for all of (for all other ) compared withother ) compared with

Case 2: Suppose the value of is such that there are recipCase 2: Suppose the value of is such that there are reciprocal lattice rocal lattice

vectors with all vectors with all within order of each other, but within order of each other, but far apart from the on the scale offar apart from the on the scale of

k

1K

01KkE

0

KkE

K

U

100 all and fixedfor ,||

1KKkUEE KkKk

k

,,,1 mKK

00 ,,

1 mKkKk EE U

0KkE

U

mKkKk KKKmiUEEi

,,,,,1,|| 1

00

Page 15: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Case 1: Case 1: nondegeneratenondegenerate perturbation theoryperturbation theory

'

''0 )(

KKkKKKkKk cUcEE

K

KkKKKkKk cUcEE

111

)( 0

|,||| on,perturbati ofspirit in the ,For 11 KkKk ccKK

)( 20

'0

''0

'0

''

11

1

11

UOEEcU

EEcU

EEcU

EEcU

c

Kk

KkKK

KK Kk

KkKK

Kk

KkKK

K Kk

KkKKKk

KKk

Kk

KKKKKkKk UOc

EEUU

cEE

)()( 30

01

11

11

Page 16: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

K Kk

KKKk UO

EEU

EE

)(||

30

20 1

1

The leading correction is of the order of The leading correction is of the order of UU22

Page 17: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Case 2: degenerate perturbation theoryCase 2: degenerate perturbation theory

mijij

iii

KKKKkKK

m

jKkKK

KKkKKKkKk

cUcU

cUcEE

,1

0

1

)(

,,,For 1 mKKK

)(1

1

2

10

'',,'1

01

UOcUEE

cUcUEE

c

m

jKkKK

Kk

KkKKKKK

m

jKkKK

KkKk

jj

mjj

Page 18: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

)(

)(

3

,0

1

1

0

1

UOcEE

UU

cUcEE

jm

ji

jijii

KkKKK Kk

KKKKm

j

m

jKkKKKkKk

)(1 2

10 UOcU

EEc

m

jKkKK

KkKk jj

The leading corrections in The leading corrections in UU is given byis given by

additional terms

micUcEEm

jKkKKKkKk jijii

,,1,)(1

0

The leading correction is of the order of The leading correction is of the order of UU but not but not UU22..

Page 19: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Energy levels near a single Bragg planeEnergy levels near a single Bragg plane

12122

21211

)(

)(0

0

KkKKKkKk

KkKKKkKk

cUcEE

cUcEE

Degenerate perturbation theory, only two reciprocal lattice vectors K1 and K2 are involved.

121, KKKKkq

KqKKqKq

KqKqq

cUcEE

cUcEE

)(

)(0

0

twotwo--level problemlevel problem

Page 20: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

0,'for ||, 0'

000 KKUEEEE KqqKqq

Page 21: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

KqKKqKq

KqKqq

cUcEE

cUcEE

)(

)(0

0

2/1

2200

00

2)(

21

KKqq

Kqq UEE

EEE

When When qq is on the Bragg planeis on the Bragg plane

Kq

Kqq

UEE

EE

0

00

Page 22: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

Energy bands in one dimensionEnergy bands in one dimension

Page 23: Bloch’s theorem - Zhejiang Universityzimp.zju.edu.cn/~yizhou/2014-Spring/Lecture-introduction-BandTheory2.pdf · Bloch’s theorem The eigenstateseigenstates of such a one-electron

SummarySummary• Bloch’s theorem

– The concept of lattice momentum– The wave function is a superposition of plane-wave states with

momenta which are different by reciprocal lattice vectors– Periodic band structure in k-space– Short-range varying potential → extra degrees of freedom →

discrete energy bands– Coherent (non-dissipative) motion of electrons in a perfect crystal

• Applicability of weak potential• The leading order correction by weak potention

– Non-degenerate case: U2 correction– Degenerate case: U correction