Can we start with that microscopic

knowledge and learn something about

bulk properties of matter ?

Will the peculiar rules governing the

behavior of an individual particle or
small group of particles
(such as the Pauli exclusion principle)
influence the properties of the matter
they compose?
 The Maxwell-Boltzmann distribution
Assumptions:
9 The particles are identical in terms of physical properties but
distinguishable in terms of position and trajectory.

9 The equilibrium distribution is the most probably way of

distributing the particles subject to the constrains of
a fixed number of particles and fixed total energy.

9 In principle, there is no limit on the numbers of particle

in a given energy state.

N, m, v P, V, T
Microscopic Macroscopic
3/2
m 2 mv2 2k BT
N v = 4N v e
2k BT

N = 0 N v dv
 A distribution of a total energy of 8E among 6 particles
20 arrangements
8E 8E (7+1) 8E (5+1+1+1)
6E 6E (6+2) 6E (4+2+1+1)
(5+3) (3+3+1+1)
4E 4E (4+4) 4E (3+2+2+1)
2E 2E 2E (2+2+2+2)
4
0 0 0 5
1
8E
8E (6+1+1) 8E (4+1+1+1+1)
(5+2+1) (3+2+1+1+1) 6E
6E 6E
(4+3+1) (2+2+2+1+1) 4E
4E (4+2+2) 4E
(3+3+2) 3 2E
2E 2E
0
5 0
0 (3+1+1+1+1+1)
2 (2+2+1+1+1+1)
 If the particles are indistinguishable, we only care about how
many particles are in each state, and there are 20 unique ways
to distribute the energy among them20 unique combinations.

If the particles are distinguishable

(make a distinction as to which particle is in which energy state),
there are 1287 unique microstates (permutations).
total particle number
Number of microstates N!
N MB =
n1!n2 !n3!... number of particle
in level i
Counting the distinguishable microstates :

8E 8E 8E
N MB N MB N MB
6E 6E 6E
6! 6! 6!
4E = 4E = 4E =
1!5! 1!2!3! 1!1!1!3!
2E 2E 2E
=6 = 60 = 120
0 0 0
We assume that each microstate (unique permutation) is
equally probable.
i.e., if there are 120 microstates that will produce a particular energy
distribution, (n1(0E)=3, n2(1E)=1, n3(2E)=1, and n4(5E)=1) p = 120
1287
then that distribution is more probable than a distribution that can
only be produced by 6 microstates, (n1(0E)=5 and n2(8E)=1). 6
p=
1287

To find the average number of particles in each state

n j = n j1 p1 + n j 2 p2 + K
average number of
particles in the the number the number of microstates
jth energy level of particles that can produce this
in each distribution divided by the
state for total number of microstates
this for all distributions
distribution
For instance,
no : the average number of particles with energy 0
Out of 20 arrangements (1287 microstates)

6 30 30 30 15
no = 5 + 4 + 4 + 4 + 4
1287 1287 1287 1287 1287
60 120 120 60 60
+ 3 + 3 + 3 + 3 + 3
1287 1287 1287 1287 1287
60 180 90 180 15
+ 2 + 2 + 2 + 2 + 2
1287 1287 1287 1287 1287
30 120 60 6 15
+ 1 + 1 + 1 + 0 + 0
1287 1287 1287 1287 1287

= 2.307
Probability of finding a particle with energy 0
p(0) = 2.307/6 = 0.385
p(Ei) : Probability of finding a particle with energy Ei

Energy Probability
level i p(Ei)
0 0.385
1 0.256
2 0.167
3 0.0978
4 0.0543
5 0.0272
6 0.0117
7 0.00388
8 0.000777

p (E j ) = 1
j

nj = N
j
 Ei
Fit data to the Maxwell-Boltzmann distribution f MB = Ae k BT

0.40

0.35

0.30

0.25
probability

0.20

0.15

0.10

0.05

0.00
0 1 2 3 4 5 6 7 8 9
Energy
 fMB(Ei) : the Maxwell-Boltzmann probability of finding a particle
with energy Ei
the probability that a state with energy Ei is occupied at
a finite temperature T.
Assuming the number of states with the same energy Ei is gi,
then the number of particles ni with energy Ei is

ni = g i f MB and N = ni
i
Total number of particles in the system

g i g (E ) density of states
For a continuous distribution E
f MB Ae k BT

ni = g i f MB n(E )dE = g(E ) f MB (E )dE

N
= 0 n(E )dE = 0 g(E ) f MB (E )dE

N = ni
i V
 Emission lines from Stellar Hydrogen
(a) Find the population of the first and second exciting states
relative to the ground state for atomic Hydrogen at room temperature,
assuming that Hydrogen obeys Maxwell-Boltzmann statistics.

Ground state : E1= 13.6eV g1= 2

First excited state : E2= 13.6eV/4= 3.4eV g2= 8
Second excited state : E3= 13.6eV/9= 1.51eV g3= 18 20000K
instead
E2
n2 g 2 e k BT g 2 (E 2 E1 ) k BT 8 (3.4eV +13.6 eV )(0.086meV/K )(300K )
= E1
= e = e
n1 k BT g1 2
g1e
= 4e 394.6 ~ 0
5.92
n3 = 4e 0.0108 T=20000K
0 Even smaller
n1 7.02
= 9e 0.0081 T=20000K
(b) Find the emission strength of the spectral lines corresponding to the
transitions E3E1 and E3E2 relative to E2E1 at 20000K
assuming equal probability of transition for E3E1, E3E2, and
E2E1.

S, strength of an emission (or absorption) line

P(if) ni
probability at the state i
transition rate from the initial state to the final state

S (3 1) P(3 1)n3 n3 0.0081

= = = = 0.75
S (2 1) P(2 1)n2 n2 0.0108
S (3 2) P(3 2 )n3 n3 0.0081
= = = = 0.75
S (2 1) P(2 1)n2 n2 0.0108
assumption
 The Maxwell speed distribution
Number of particles per unit volume v y
with energy from E to E+dE v
v = constant
n(E )dE = g (E ) f MB (E )dE
Density of states the distribution function vy
in the interval probability that a v x
vz
from E to E+dE particle with energy E vx

1 v
Ideal gas of E = mv 2 v z
dv
point particles 2
mv 2
n(E )dE = g (E )Ae 2k B T
dE
3/ 2
4N m mv 2
n(v )dv = ? n(v )dv = v 2e 2k B T
dv
V 2k BT
Number of particles per unit volume with velocity from v to v+dv
Space change : energy space velocity space

g (E )dE Density of states in the interval from E to E+dE

f (v )dv = C4v 2 dv Density of states in the interval from v to v+dv
N mv 2
= 0 n(E )dE = 0 C4v 2 Ae
2k B T
dv
V
2 j az 2 1 3 5... (2 j 1)
using
z e dz = where j=1,2,3,
0
2 j +1 a j a
3/ 2
N m
CA =
V 2k BT
3/ 2
4N m mv 2
Maxwell speed n(v )dv = v 2e 2k B T
dv
distribution V 2k BT
1859
 vn(v )dv

The average speed v= 0
N /V
3/ 2
2k BT m 3 mv 2

most probable speed v mp = = 4 0 v e 2k B T

dv
m 2k BT
dn(v )
=0 8k BT
dv v mp =
m

The root mean square speed

v n(v )dv
1/ 2
2
v rms = v =
2 0

N / V 1/ 2
m 3/ 2
mv 2
= 4 dv

ve
4 2k B T
2k BT 0


3k BT
=
m
z The peak shifts to the right as T increases
The average speed increases with increasing T.

z The shape is asymmetric.

As the temperature increases,

this curve broadens and extends to higher speeds.
 3k BT
Using: v rms = v = 2

m
1 3
The equipartition theorem m v = K = k BT
2

2 2
A classical molecule in thermal equilibrium has an
average energy of kBT/2 per degree of freedom.

But generally, there are more than three degrees of freedom (more than
just the translational motion in each of x, y, and z):

1 2 For molecules that can rotate, you can have a

E rotation = I rotational degree of freedom.
2
1 1 2 A one dimensional harmonic oscillator has
E = mv x + kx
2
two degrees of freedom, one corresponding to
2 2 its potential energy, the other to its kinetic energy.

An energy kBT/2 is associated with each degree of freedom.

 Problem with the Maxwell-Boltzmann distribution ?
Distinguishability

In classical dynamics, particles can be identical but distinguishable.

Each trajectory of individual particle can be traced.
Maxwell-Boltzmann distribution is applicable.
1/ 3
uncertainty in x << d The average distance V
particle position between particles

N
wavefunctions of two particles do not overlap

In quantum mechanics, particles exhibit wave-like properties and

are necessarily fuzzy.
They are not distinguishable when they are close together.
Quantum statistics is required.
 2
p x = p p x = mk BT 0
2
x

uncertainties h2 h2
x =
p x mk B T
1/ 3

x << d
h V
<<
2 mk BT N
For MB distribution N h3
<< 1
V 8(mk B T )3/ 2

Ex. Hydrogen gas at STP

N h3
V 8(mk BT )3 / 2

=
6.02 10 23
( 34
1.055 10 Js ) 3

(
22.4 10 3 m 3 8 2 1.67 10 27 kg 0.086meV/K 273K 1.6 10 19 J/eV )
3/ 2

=8.8410 8 <<1 The MB statistics is valid.

Ex. Conduction electrons of Ag at T=300K

N m 10.5g/cm 310 6 cm 3 /m 3
= NA = 6.02 10 23 /mole =5.8610 28 /m3
V A 107.9g/mole

N h3
V 8(mk B T )3 / 2

= 5.86 10 28 m 3
(1.055 10 34
Js )
3

(
8 0.91 10 30 kg 0.086meV/K 300K 1.6 10 19 J/eV )
3/ 2

=37.2 <<1
The MB statistics is invalid.
Quantum statistics is required.
 Quantum statistics
System of many identical and indistinguishable particles.
wavefunctions of particles overlap
interchangeable
The simplest case a two particle system
r r
a ( r1 ) b ( r2 ) One in state a at r1, the other in state b at r2.
r r
a ( r2 ) b ( r1 ) One in state a at r2, the other in state b at r1.

w/. consideration of indistinguishability

1
B = [ a (rr1 ) b (rr2 ) + a (rr2 ) b (rr1 )] symmetric function
2
boson
1 r r r r
F = [ a (r1 ) b (r2 ) a (r2 ) b (r1 )] anti-symmetric function
2
fermion
When both particles are switched, B2 and F2 remain the same.
Consider two particles at the same state a,

Maxwell-Boltzmann result for distinguishable particles

r r r r r 2 r 2
MB MB = a ( r1 ) a ( r2 ) a (r1 ) a ( r2 ) = a (r1 ) a ( r2 )

Bose-Einstein result for bosons

2
1 r r r r
B B =

( a (r1 ) a (r2 ) + a (r2 ) a (r1 ))
2
1
( r 2 r 2
) r 2
= 4 a ( r1 ) a (r2 ) = 2 a ( r1 ) a ( r2 )
2
r 2
= 2 MB

MB
Bosons are twice as probable to occupy the same state as
distinguishable particles.
Bose-Einstein condensation (BEC)

In 1995 this Einsteins prediction was directly confirmed.

A BEC in a cloud of rubidium atoms at T<100nK by Cornell and Wieman.
Bose-Einstein condensation (BEC) 2001
A state of matter formed by Bosons
cooled below a critical temperature Tc.
A large fraction of atoms collapse into
this lowest quantum state.
2/3
n h2
Tc =
2.6124 2 mk B Wolfgang
Wieman Cornell
B: 1951 B: 1961 B: 1957
Theoretical works : Einstein and Bose NIST
U. Of Colorado
(1925)
The first pure BEC was
A sharp peak at v=0
created in 1995.
(ground state)
Tc = 190nK for T < Tc.
N T~50nK

vx T~200nK
vz
T~400nK velocity distribution
of a gas of 2000 87Rb atoms
 Fermi-Dirac result for fermions
2
1
F F = ( a (rr1 ) a (rr2 ) a (rr2 ) a (rr1 )) =0
2
It is impossible that two fermions occupy the same state.

Pauli exclusion principle

Theoretical works : Fermi and Dirac

(1926)
In 1926 Fowler used it to describe the
collapse of a star to a white dwarf.
In 1927 Sommerfeld used it to describe
the electrons in metals.
 Quantum statistics
identical and indistinguishable particles

boson fermion
Integral spin Half integral spin

Bose-Einstein distribution Fermi-Dirac distribution

1921 1938 1933

Fermi Dirac
1894~1974 1879~1955 1901~1954 1902~1984
A distribution of a total energy of 8E among 6 indistinguishable particles

The average number of particles with energy 0 Out of 20 arrangements

Bose-Einstein distribution
1 1 1 1 1
no = 5 + 4 + 4 + 4 + 4
20 20 20 20 20
1 1 1 1 1
+ 3 + 3 + 3 + 3 + 3
20 20 20 20 20
1 1 1 1 1
+ 2 + 2 + 2 + 2 + 2
20 20 20 20 20
1 1 1 1 1
+ 1 + 1 + 1 + 0 + 0
20 20 20 20 20
= 2.45
Probability of finding a particle with energy 0
p(0) = 2.45/6 = 0.408
 p(Ei) : Probability of finding a particle with energy Ei

Energy Probability
level i p(Ei) 0.40

0 0.408 0.35

1 0.258 0.30

2 0.150 0.25

probability
3 0.075 0.20

4 0.050 0.15

5 0.025 0.10

6 0.0167 0.05

7 0.00833 0.00
0 1 2 3 4 5 6 7 8 9
8 0.00833 Energy (E)

Both Bose-Einstein and Maxwell-Boltzmann distributions

give the similar but not identical results.
In general, the Bose-Einstein distribution tends to have more
particles in the lowest energy levels than other distributions.
Fermi-Dirac distribution
w/. consideration of spin
No more tan two fermions occupy the same energy state.
A distribution of a total energy of 8E among 6 particles
20 arrangements
8E 8E 8E 8E
3 only
6E 6E 6E 6E
4E 4E 4E 4E
2E 2E 2E 2E

0 0 0 0
1
1 1 1
no = 2 + 2 + 2 = 2.0
3 3 3
Probability of finding a particle with energy 0
p(0) = 2.0/6 = 0.333
 p(Ei) : Probability of finding a particle with energy Ei

Energy Probability
level i p(Ei) 0.40

0 0.333 0.35

1 0.278 0.30

2 0.167 0.25

probability
3 0.167 0.20

4 0.055 0.15

0.10
5 0
0.05
6 0
0.00
7 0 0 1 2 3 4 5 6 7 8 9
8 0 Energy (E)

The Fermi-Dirac distribution shows a leveling off of probability

at both low and high energies compared with other distributions.
For a large number of quantum particles,
a nearly continuous distribution function
1
f BE (E ) = Concentration
E/k B T
1
0 n(E)dE = 0 g(E) f (E )dE = N/V
Be
1
f FD (E ) =
He E/k BT + 1 # of particles density of states
(energy)(volume)
# of states
(energy)(volume)

N g(E)
= 0 g (E ) f BE (E )dE = 0

dE
V Boson Be E/k B T
1
N g(E)
=

0 g ( E ) f (E )d E =

0 dE
E/k B T
+1
FD
V Fermion He

1 1
f FD (E ) = f BE (E ) =
e (E E F )/k BT + 1 e E/k BT 1
Fermi-Dirac distribution Bose-Einstein distribution
 1
f MW (E ) =
e E/k BT

1
f BE (E ) =
e E/k BT 1
When E>>kBT, fBE(E) fMW(E) Due to the
When E<<kBT, fBE(E) is bigger than fMW(E) indistinguishability
of particles
 1 Due to the
f FD (E ) = indistinguishability
1.1
e (E E F )/k BT + 1 of particles
1.0
T=0.01TF
0.9
0.8 T=0.02TF
0.7
fFD(E) 0.6 T=0.05TF
0.5 T=0.5TF
0.4
0.3 T=1.0TF
0.2
0.1
0.0 E(A.U.)
0 2 4 EF 6 8 10

When E EF >>kBT, fFD(E) fMW(E)

When T=0, fFD(E)=1 for E<EF and fFD(E)=0 for E>EF
When T 0,
fermions are excited from below EF to above EF with increasing T.
 Applications of Bose-Einstein statistics
1. Blackbody radiation
2. Specific heat of solids : phonon contributions

The energy density of photon with energies from E to E+dE

g (E)E
u (E )dE = En(E )dE = E/k BT dE
e 1
number of allowed values in Chapter 3
frequency range from f to f+df
2
2af 2a 8V 2
N( f )df = d f = 3
f df
c c c
Transfer to f domain 8V 2
= E dE
(hc )3

N (E )
E=hf
dE = g (E )dE
V
8 2 8 E3
g (E ) = E and u (E )dE = dE
(hc )3
(hc ) e 1
3 E/k B T
Number of photons per unit volume inside a cavity at a finite T.
8 E2
= 0 n(E )dE = 0 g (E ) f (E )dE = 0
N
dE
V (hc ) e 1
3 E/k B T

8 (k BT ) (E k BT ) 8 (k BT ) z 2
3 2 3
= 0 E/k BT d (E k BT ) = 0 z dz
(hc )3
e 1 (hc )3
e 1
2.40
3
N 8k 3
3
1.38 10 23 J/K 3
= 2 .4 B
T = 2.4 8 T
V (hc )
3
( 34
)(
6.63 10 Js 3 10 m/s
8
)
= 2.02 107 T 3 m 3

T=3000K
N
= 5.45 1017 m 3
V

T=3K
N
= 5.45 108 m 3
V
2. Specific heat of solids : phonon contributions
dU
The Molar Specific Heat CV = [cal/mole-K]
dT
A solid Using the classical equipartition theorem
Three dimensional harmonic oscillator of atom
K.E. + U
6 degrees of freedom 5.97 [cal/mole-K]
k BT dU
U = 6 NA and CV = = 3k B N A = 3R
2 dT

Experimental data show that

z At high temperatures,
CV becomes a constant, ~3R

z As T approaches 0, the molar

specific heat approaches 0
 Classical theory

Diamond,
C (cal/mole-K)

Experimental data red points

Einsteins model blue curve
w/. D=1320K
Ann. Physik 22, 180 (1907)

T/D
1907, by Einstein
The quantized energies of vibrating atoms in solid must be
explicitly considered at low temperatures.

The average energy of a 1D oscillator

h with frequency at temperature T,
E = h/k BT
e 1 obeying the Bose-Einstein distribution
 h
U = NA 3 E = 3 NA
e h / k B T 1
2 h / k B T 2
dU h e h e h / k B T
CV = = 3 N A k B = 3R
dT k T
B e
h / k B T
1
2
k T
B e (
h / k B T
1
2
) ( )

1.0
high T: CV 3NkB
0.8
same as the
CV (3NkB)

0.6 Dulong and Petit value

correct trend with T .

0.4

0.2
low T: CV 3NkB (h/kBT)2 e-h/kT
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
-1
x = kBT / h
 1936
Data taken by Walther Nernst (chemistry)

Ag
C (cal/mole-K)

Peter Debye,
Einsteins model 1884-1966

T (K)
At low T, there are systematic deviations between data and Einstein model.
Einstein realized that the oscillations of a solid are complex,
far from single frequency.

In the Einstein model, C decreases too rapidly at low temperatures.

Debye model gives correct T3 dependence of C at low T.
An application of Fermi-Dirac statistics :
The free electron gas theory of metals

Not interacting electrons

(except w/. walls of the box)

P 2 (hk )
2
= K.E. = =
2m 2m
Electrons are bound in the metal ( a volume).
Boundary conditions A nearly continuous distributed
energy levels (states)
How to accommodate N electrons in the energy levels ?
Pauli exclusion principle + spin degeneracy (two spins per level)
Start to fill the levels from the bottom (n=1) and continue to fill higher levels
with electrons until all N electrons are accommodated.
1,, nF, where nF is the value of n for the uppermost filled level.
 In a metallic cube,
Schrdinger equation for the free electrons 0
h2 2 2 2
2 + 2 + 2 + U(x, y, z) =
2m x y z
Boundary condition : is periodic in x, y, and z with period L
2 4 2 4 2 4
k x = 0, , ,... ; k y = 0, , ,... ; k z = 0, , ,...
L L L L L L
One state every k-volume interval kx ky kz=(2/L)3
only one spin 3
1 1 L V
G(k) = = = =
k x k ykz (2 /L) 2 (2)3
3

G(k)4 k 2dk 1 1
g( E )dE = = 4 k 2
dE
density of states
V (2) 3
dE / dk
1 (2m) E
# of states 3
4 k 2 m # of states per unit
per unit energy = dE = dE
per unit volume (2)3 h 2k 4 2 h3 volume w/. energies
from E to E+dE
 3/ 2
1 2m
g( E ) = 2 2 E density of states in three dimensions
2 h
Ground states T=0, Fill energy level from bottom : 2 per level
En
highest level occupied w/. EF
EF
Maximum energy : EF = h2kF2/2m
E4
E3
E2
E1
D(E)
N
n = = g(E) f (E)dE EF
V 0
EF F
1 E
= g(E)dE
0
f(E)
EF =
h2
2m
(2 2/3
3 n ) 0
1

E
n F TF
Finite temperatures T0
Kinetic energy of electron increases due to the increase of thermal energy
occupy higher energy levels
Electrons are Fermions : quantum effects such as Pauli exclusion principle
1
f FD (E ) =
e (E E F )/k BT + 1
Fermi-Dirac distribution

1.1
fFD(E) 1.0
0.9
0.8
T=0.01TF
EF =
h2
2m
( 3 n)
2 2/3

0.7
0.6 T=0.02TF k BTF
0.5 T=0.05TF
0.4
0.3
0.2
0.1
0.0 E
0 2 4 EF 6 8 10
 EF
n = dE g (E) f (E) = dE g (E)
0 0
U(T) = dE D(E ) f ( E , T) E = U(0K) + U(T) EF EF
0 + dE E F g (E) f (E) = dE E F g (E)
0 EF 0

EF
U = dE (E - E F ) g (E) f ( E ) + dE (E E F ) g (E)(1 f (E) )
EF 0

dU f (E , T)
Ce = = dE (E E F )g (E)
dT 0 T
In general, T/TF<0.01, df/dT has non-zero value within couples of kBT
g(E) is about g(EF) in the energy regime EF kBT
f (E , T)
C e = g(E F ) dE (E E F ) f (E, T) d 1
T =
( )
0
x T dT exp ( E E ) /( k T) + 1
e E F B
C e = g (E F )k BT dx x
2 2

E F /k B T ex + 1 (
2
= )(E E F ) exp((E E F ) /( k BT) )

k BT 2 (exp((E E F ) /(k BT) ) + 1)2
ex x ex E EF
C e = g (E F )k T dx x
2 2
= where x =
B
- (e x
+1 )
2
(
T ex + 1 2 ) k BT

ex 2
- dx x e x + 1 2 = 3
2

( )
2 2
3N 2
C e = g(E F )k 2BT = k BT
3 3 2k BTF
1 2 T Free electrons contribution to
= Nk B T heat capacity
2 TF
U
Ce

T T2

0.6NF

T T
In general, when T<<D and T<<TF=EF/kB
C = T + AT3 sum of electron and phonon contributions
 Low Temperature regime

Phys. Rev. 91, 1354

KCl
CV/T (Joule Mole-1K-2)

(1953)

Low Temperature
Solid State Physics
(1963)
Cu

T2 (K2)