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Branislav K. Nikolić

Department of Physics and Astronomy, University of Delaware, U.S.A.

http://www.physics.udel.edu/~bnikolic/teaching/phys624/phys624.html

Condensed Matter Systems

Colloidal Polymer

Dispersions Melts and

Crystalline Solids Non-Crystalline Solutions

(Metals, Insulators, Solids

Semiconductors) Liquid

Crystals

Crystalline

Solids + Quasicrystals Amorphous Biomatter

Defects Solids (Glass) (proteins,

(point, membranes,

dislocations, Polymer nucleic acids)

surfaces and Solids (Glass

interfaces)

and Rubber)

Basic Notions of Condensed Matter

as individual particles as possible - modern

condensed matter theory asserts that a solid

crystal is actually a gas of weakly interacting

quasiparticles.

Scalar Bosons (Spin=0)

→

Phases of matter are characterized by the symmetry of their

ground (lowest energy) state (Landau, 1937).

Classical (at T>0) and Quantum (at T=0).

Quasiparticles vs Collective Excitations

excitation, corresponding to

consisting of a real coherent motion of all the atoms

electron and the cloud of in the solid. It is quantized

effective charge of

opposite sign due to

qe− lattice vibration with a typical

energy scale ℏω ∼ 0.1eV

exchange an correlation

effects arising interaction

Exciton: bound state of electron

with all other electrons in

and hole with binding energy10eV

the system. The electron is

a fermion with spin ½. The

Plasmon: longitudinal charge

Fermi energy (highest

oscillations of the entire electron

occupied state) is of the

gas relative to the lattice of ions

order of 5 eV and the

due to the long-range nature of the

Fermi velocity is 108 cm/s,

Coulomb interaction

so it can be treated like a

nonrelativistic particle. The

mass of quasiparticle can Magnon:

be substantially different Polaron: a quasiparticle, like electron, whose motion collective

than that of the free in polar crystals distorts the lattice of positive and excitation of

electron. negative ions around it – polaron has different mass the spin

than the electron. degrees of

freedom on the

Hole: a quasiparticle, like the electron, but of opposite charge; it corresponds to the absence crystalline

of electron for a single-particle state which lies below the Fermi level. The notion of a hole is lattice with an

particularly convenient when the reference state consists of a quasiparticle states that are energy scale

fully occupied and are separated by an energy gap from the unoccupied state. ℏω ∼ 0.001−0.1eV

Experimental Probes of Condensed Matter

Phases and Quasiparticle Dynamics

Scattering: Send neutrons or X-rays into the system with

prescribed energy and momentum; measure the energy and

momentum of the outgoing neutrons or X-rays.

NMR: Apply static magnetic field B and measure absorption

and emission of magnetic radiation at frequencies of the order

geB

of ω c = .

m

Thermodynamics: Measure the response of macroscopic

variables (energy, volume, etc.) to variations of the temperature,

pressure, etc.

Transport: Set up a potential ∇ϕ or thermal gradient ∇T and

measure the electrical or heat current. The gradients can be

held constant or made to oscillate at finite frequency.

PHYS 624: Introduction to Solid State Physics

Quantum Hamiltonian of

Condensed Matter Physics

“”The general theory of quantum mechanics is now almost complete. The

underlying physical laws necessary for the mathematical theory of a

large part of physics and the whole of chemistry are thus completely

known, and the difficulty is only that the exact application of these laws

leads to equations much too complicated to be soluble.”

P. A. M. Dirac 1929

2 NN

2 NN

P e Zn Zm Quantization

H= ∑

ˆ n

+ ∑ ∂ ∂

n=1 2M 2 n≠m=1 | Rn − Rm | p ≡ −iℏ , P ≡ −iℏ

n

∂r ∂R

TN : motion of nuclei VN −N : interaction between nuclei

Ne

pi2 e2 Ne 1 NN Ne

Zn

+ ∑

i =1 2Mi

+ ∑

2 i≠ j =1 | ri − rj |

− e ∑∑

2

n=1 i =1 | Rn − ri |

Te : motion of electrons Ve−e :int eraction between electrons Ve−N :interaction between electrons and nuclei

Complexity in Solid State Hamiltonian

Even for chemist, the task of solving the

Schrödinger equation for modest multi-

electron atoms proves insurmountable

without bold approximations.

physicist is qualitatively more severe:

23

N N ∼ Ne ∼ 10

−2

Energy scales: 10 eV − 10 eV 4

The Way Out:

Separate Length and Energy Scales

Energy: ω , T < 1 e V

ℏ ℏ

Time: ∆τ ∼ ∼ −19

∼ 1 0 −15

s

1eV 10 J

Length: | x i − x j |, q − 1 ≫ 1 Å

forget about atom formation + forget about crystal formation

me

+ Born-Oppenheimer approximation for ≪1

mN

⇓

Hˆelectronic =Tˆe +Vˆe−I +Vˆe−e, Vˆe−I (r +rn) =Vˆe−I (r), rn = n1a1 +n2a2 +n3a3

PHYS 624: Introduction to Solid State Physics

“Non-Interacting” Electrons in Solids:

Band Structure Calculations

In band structure calculations electron-electron interaction is

approximated in such a way that the resulting problem becomes an

effective single-particle quantum mechanical problem …

b (r )

N e

i =1

n(r′)

H Hartree = Te + Ve− I + e ∫ dr′

ˆ ˆ ˆ 2

, n(r) = ∑ | φkHb (r) |2 = n(r + rn )

| r − r′ | ε H ( k ,b )≤ EF

n (r′) δ ELDA

xc [ne ]

HLDA = HIE (r) + e ∫ dr′

ˆ ˆ 2

+ , ExcLDA[ne ] = ∫ dr n(r)excLDA (n(r))

| r − r′ | δ n(r)

PHYS 624: Introduction to Solid State Physics

From Many-Body Problem to Density Functional

Theory (and its LDA approximation)

SE Ψ ... Ψ

V (r ) ⇒ Ψ (r1 ,… , rNe ) ⇒ average of observables

Example: Particle density

n0 (r ) ⇒ Ψ 0 (r1 ,… , rNe ) ⇒ V (r )

Ψ 0 (r1 ,… , rNe ) ≡ Ψ 0 [ n0 (r )]

PHYS 624: Introduction to Solid State Physics

Pauli Exclusion Principle for Atoms

Without the exclusion principle all electrons would occupy the same atomic orbital.

There would be no chemistry, no life!

Many-Body Wave Function of Fermions

“It is with a heavy heart, I have decided that Fermi-Dirac, and not

Einstein is the correct statistics, and I have decided to write a short

note on paramagnetism.” W. Pauli in a letter to Schrödinger (1925).

All electrons in the Universe are identical two physical situations that

→

differ only by interchange of identical particles are indistinguishable!

Pij Ψ ( x1 ,… , xi ,… , x j ,… , xn ) = Pij Ψ ( x1 ,… , x j ,… , xi ,… , xn )

Pˆij Hˆ = HP

ˆ ˆ ← Ψ Aˆ Ψ = Ψ Pˆ † AP

ij ij

ˆ ˆ Ψ ⇔ Pˆ Aˆ = AP

ij

ˆˆ

↑

+ ΨA , Pˆα is even

ΨS ΨA Pˆα ΨS = ΨS , Pˆα ΨA =

− ΨA , Pˆα is odd

1

Pα A Ψ = A Ψ , A = ∑εα Pˆα

ˆ ˆ ˆ ˆ

N! α

PHYS 624: Introduction to Solid State Physics

Pauli Exclusion Principle for Hartree-

Fock or Kohn-Scham Quasiparticles

“There is no one fact in the physical world which has greater impact

on the way things are, than the Pauli exclusion principle.” I. Duck and

E. C. G. Sudarshan, “Pauli and the Spin-Statistics Theorem” (World

Scientific, Singapore, 1998).

Two identical fermions cannot occupy the same quantum-mechanical state:

Hˆ = hˆ1 + hˆ2 + … + hˆN

hˆi φi = ei φi ⇒ Hˆ Φ1,2,…, Ne = E1,2,…, Ne Φ1,2,…, Ne

E1,2,…, Ne = e1 + e2 + … + eNe

φ1 (1) … φN (1)

e

1 1

Φ1,2,…, Ne = ⋮ ⋱ ⋮ ⇒ nkσ =

N! e(εkσ −µ )/ kBT + 1

φ1 ( Ne ) ⋯ φN ( Ne ) e

Energy Bands and Rigid Band Filling

Insulator Semiconductor Semimetal Metal

Electron-Electron Interactions in Metals

Bloch theory of electrons in metals: completely independent

particles (e.g., even more sophisticated Hartree-Fock fails badly

because dynamic correlations cancel miraculously exchange effects).

Why is long-range strong (of the order of kinetic energy) Coulomb

interaction marginal in metals?

1. In system with itinerant electrons, Coulomb interaction is very

−1

effectively screened on the length scale of kF .

2. In the presence of Fermi surface the scattering rate between

electrons with energy E F + ℏω vanishes proportional to ω 2

since the Pauli principle strongly reduces the number of scattering

channels that are compatible with energy and momentum

conservations – Landau “quasielectrons” live very long!

DFT (and LDA) only describes an equivalent one-electron substitute system with the same ground-

state energy and electron density. Altough we may expect that the ground-state properties are

reasonably described, the wave functions and excitation energies (band structures) may be used only

if the prerequisites of the Landau Fermi Liquid theory are fulfilled.

Real Free Electrons vs. Landau Quasielectrons

made of very large number of

Ψ(t ) ∼ e−iE ( k )t ℏ Ψ(t ) ∼ e−iE ( k )t ℏe−t τ exact eigenstatates of the

interacting system. The separation

of these states is exponentially

small in the system size and thus

irrelevant physically for

reasonable systems. The cluster

of all these states form the

quasiparticle with its average

enery and lifetime (= inverse of

the energy broadening).

Exchange-Correlation Hole

Surrounding every electron in a solid there's an

exclusion zone, called the exchange-correlation

hole, into which other electrons rarely venture.

This is the hole around an electron near the centre

of a bond in silicon.

From Weakly to Strongly Correlated

Electrons

Exchange and Correlation in 3D gas of noninteracting fermions:

3 n sin x − x cos x

2

g σ ,σ ( r , r ′) = −

2 x3

g σ , − σ ( r , r ′) = 0, x = k F | r − r ′ |

Correlated Electron System: g σ , − σ ( r , r ′) ≠ 0

Strongly Correlated Electron System: gσ,σ (r,r′) ∼ gσ,−σ (r,r′)

Example of novel strongly correlated matter:

PHYS 624: Introduction to Solid State Physics

Survival of Long-Range Coulomb

Interaction: Collective Excitations

4πne2

ℏωp ≃ℏ ∼ 5− 20eV

me

k k +Q

Q

into two independent sets of excitations (progenitor of the

idea of renormalization!) high energy plasmon →

→

Breaking the Symmetry

QUESTION: In QM we learn that the ground state must have the symmetry

of the Hamiltonian - so there can't be a dipole moment (interactions between

ions and electrons have no preferred direction in space). On the other hand,

ammonia molecule obviously has dipole moment?

RESOLUTION: The ammonia molecule

ground state is a superposition of states,

so as to recover the symmetry

of the Hamiltonian. However, at short

time-scale molecule can be trapped in one

of the states (due to large potential

barrier for tunneling between the states),

and we measure non-zero dipole moment.

QUESTION: What about larger molecules ( > 10 atoms) which have definite

three-dimensional structures which break the symmetry of the Hamiltonian?

RESOLUTION: We cannot understand the structure of molecules

starting from Quantum Mechanics of elementary particles - we need

additional theoretical ideas (emergent phenomena)!

PHYS 624: Introduction to Solid State Physics

Broken Symmetries and Phases of Matter

underlying microscopic equations.

Example: Water exhibits full translational and rotational symmetry

of Newton’s or Schrödinger’s equations; Ice, however, is only invariant

under the discrete translational and rotational group of its crystal

lattice translational and rotational symmetry of the microscopic

→

Order Parameter Paradigm (L. D. Landau, 1940s): Development

of phases in a material can be described by the emergence of an

"order parameter“ (which fluctuates strongly at the critical

point):

iϕ

M , Ψ(r) = ρs e , ρtypical (ω, r)

PHYS 624: Introduction to Solid State Physics

Crystalline Hard Condensed Matter Phases

it is energetically favorable to break the symmetry in the same way in

different parts of the system because of broken symmetries the

→

solids are rigid (i.e., solid) and exhibit long-range order.

In crystalline solids discrete subgroups of the translational and

rotational group are preserved

metals insulators

T →0⇒σ ≠ 0 T →0⇒σ →0

ρ ρ

T T

PHYS 624: Introduction to Solid State Physics

Broken Symmetry States of Metals

k e n U(1)

Bro Highly

Anisotropic

Superconductors

T < Tc ⇒ σ → ∞ Charge-Density Wave

+ Meissner effect

Spin-Density Wave

Broken Spin Rotational Symmetry of

Metals and Insulators

ro n

ts

An

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rant Elect

tif

Fe

ag

rri

M

Magnetism

err

rg ma

gn

ets

om

e

nb

ine

agn

se

It

ei

et

r

H

n e

s

Sto

Ground state symmetry determines the properties of collective excitations – Spin waves (Magnons)

Non-Crystalline Hard CM Phases:

Quasicrystals

Among the most well known consequences of periodicity is the fact that the

only rotational symmetries that are possible are 2-, 3-, 4-, and 6-fold

rotations ⇒ Five-fold rotations (and any n-fold rotation for n>6) are

incompatible with periodicity.

Quasicrystals =quasiperiodic crystals [D. Shechtman, I. Blech, D. Gratias,

and J.W. Cahn, "Metalic phase with with long-range orientational order and no

translational symmetry," Phys. Rev. Lett. 53, 1951 (1984) ]: Translational order

completely broken; rotational symmetry broken to 5-fold discrete subgroup.

Penrose tile is a 2D example

of a quasicrystal: There is

perfect long-range order and

no periodicity in the normal

sense.

though they are all alloys of two or three metals they

are very poor conductors of electricity and of heat.

Imaging Quasicrystals via STM

Penrose tiling overlaid [Ledieu et al., Phys. Rev. B 66, 184207 (2002)]

Non-Crystalline Hard CM Phases:

Glasses

Glasses: rigid but random arrangement of atoms; in fact, they are

“non-equilibrium phase” – effectively they look more like a frozen

“snapshot” of a liquid. The structural glassy materials arise when a

liquid is cooled to an amorphous solid fast enough

to prevent crystallization, which would otherwise

occur if the time had been sufficient for the

sample to reach true equilibrium at each

temperature. Thus, “frozen” supercooled liquids

(which have enormous viscosity that prevents

any large-scale flow on human time scales) form

a glassy state of matter that is substantially

different from crystals: it is disordered and

only metastable thermodynamically. Moreover,

the essential physics of nonequilibrium glassy

state (leading to rapid increase in response time,

and phenomena like aging, rejuvenation, memory

effects, …) is the prototype of a slow

nonexponential relaxation found in diverse

physical systems: spin glasses, disordered

insulators (Coulomb glass), magnets,

superconductors, proteins, colloidal suspensions,

Example: Amorphous Silicon. granular assemblies, …

Soft Condensed Matter Phases

Liquids (full translational and rotational group preserved) vs.

Solids (preserve only a discrete subgroups).

Liquid crystalline phase – translational and rotational symmetry

is broken to a combination of discrete and continuous subgroups:

reaction can take place which cross-links them, thereby forming a gel.

Broken Symmetries and Rigidity

Phase of a Cooper pair develops a rigidity it costs energy to bend

→

phase superflow of particles is directly proportional to gradient of

→

phase:

1

ρ s [∇ φ ( x ) ] ⇒ j s = ρ s ∇ φ s

2

U (x) ∼

2

Phase Broken Rigidity/Superflow

Symmetry

crystal translation Momentum (sheer stress)

superfluid gauge matter

superconductivity EM gauge charge

F- and AF-magnetism spin rotation spin (x-y magnets only)

nematic liquid crystal rotation angular momentum

? Time Energy?

translation

High Energy Physics:

Lessons from Low Energy Experiments

Anderson Higgs

Mechanism

Asymptotic

Freedom in the

Physics of

Quark

Confinement

PHYS 624: Introduction to Solid State Physics

Quantum Critical Matter

Complexity and Quantum Criticality in

Transition Metal Oxides Strongly Correlated Materials

Complexity and Diversity of

Crystalline Phases

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