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MECHANICS
•statistical distributions – general considerations
•Maxwell-Boltzmann
•Bose-Einstein
•Fermi-Dirac
•Maxwell-Boltzmann statistics
•Maxwell-Boltzmann distribution
•energies in an ideal gas
•equipartition of energy
•quantum statistics
•fermions and bosons
•Bose-Einstein and Fermi-Dirac distribution
•comparison of the three statistical distributions
•applications
•Planck radiation law
•specific heats of solids
•free electrons in a metal
general considerations
central question: how does the behavior of a many-particle system
depend on the properties of the single particles?
but: too many single particles to describe them one by one
particles interact “weakly” with one another and the container walls
thermal equilibrium but no correlation
the surface i
defined by an
equation of i
states 2
1
2
1
i etc., etc., etc. ...
i
2
2 1
1
An ensemble is a collection of a large number of replicas (or mental copies) of the microstates of
the system under the same macroscopic condition or having the same macrostate. However, the
microstates of the members of an ensemble can be arbitrarily different. Thus, for a given macroscopic
condition, a system of an ensemble is represented by a point in the phase space. The ensemble of a
macroscopic system of given macrostate then corresponds to a large number of points in the phase
space.
statistical distributions
most easy case:
•thermal equilibrium
•constant energy (E=const.)
•constant number of particles (N=const., for “classical” particles)
n()=g( )f()
probability of occupancy
number of particles of each state with energy
with energy (distribution function) or average
Number of particles in each state of
number of states Energy
with energy
(statistical weight)
statistical distributions
classical system:
d , etc. g()d
•identical particles
•identical particles •identical particles
•integral spin
•“far” apart •odd half-integral spin
(bosons)
(no overlap of Y) (fermions)
•close together
•close together
(overlapping Y)
(overlapping Y)
distinguishable
indistinguishable
indistinguishable
statistical distributions
fMB()=A e-/kT
321 411
312 141
213 114
231 3 ways
123
132 more likely
6 ways
energies in an ideal gas
ideal gas:
•PV=RT
•N is large
•translational motion, quantization is irrelevant
2N / kT
n()d 3/ 2
e d
(kT )
(energy distribution)
KT
n Ag e
n d C e KT d
C 2 ABm 3
Total number of molecules is N
2
N n d C
0
0
e KT d
C 3 2N
KT 2 C 3
2 KT 2
ax 1
0
xe dx
2a a
SO , n d
2 N
e
KT
d
3
KT 2
2N 3 2
3
KT KT
3
KT 2 4 2 e ax dx 3
3
0
x
4a 2 a
NKT
2
E
SO AVERAGE MOLECULAR ENERGY,
N
3
KT
2
Most probable energy
dn
0
d
Molecular speed distribution
n d
2 N
e
KT
d
3
KT 2
1 2
mv , d mvdv
2 2
mv
2 N m 2 KT
n v dv 3
ve mvdv
KT 2 2
mv 2
3 2
2m N 2 2 KT
3
v e dv
KT 2
3 2 mv 2
m 2 2 KT
4 N v e dv
KT
Molecular speed distribution
1. Mean velocity:
vnv dv vnv dv
v
0
0
8KT
1.59
KT
N m m
nv dv
0
1. Root mean square velocity:
2 3KT
vrms v
m
1. Most probable velocity:
dnv 2 KT
v p when 0, vp
dv m
Here’s a plot of
the distribution:
Notice how “no” molecules have E=0, few molecules have high
energy (a few kT or greater), and there is no maximum of
molecular energy.
k has units of [energy]/[temperature] so kT has units of energy.
Here’s how the distribution changes with temperature (each
vertical grid line corresponds to 1 kT).
ε = kT ,
2
Example 9.4 Find the rms speed of oxygen molecules at
0 ºC.
3kT
v rms =
m
3 1.38×10 J/K 0+273 K
-23
vrms =
5.31×10 -26
kg
bosons:
•integral spin (0,1,2,…)
•symmetric wave function
(exchange of two bosons does not change the system)
•all bosons can be in the same quantum state
•Photons, Phonons
•Wave function of system of boson is not affected by any
exchange of any pair of particle
1
f BE () / kT
Ae 1
FERMIONS
odd half integral spin (1/2,3/2,5/2,…)
• antisymmetric wave function
– (exchange of two fermions changes symmetry of the
system)
• only one fermion can be in a quantum state
– (exclusion principle, Pauli principle)
• probability for two particles in one state: 0!
1
f FD () / kT
Ae 1
1 F / kT
f FD () (F ) / kT
, Ae
e 1
Bose-Einstein / Fermi-Dirac distribution
bosons:
one boson of a system in a certain state increases the probability
of finding another boson in this state!
fermions:
one fermion of a system in a certain state prevents all other
fermions from being in that state!
1 1
f BE () / kT
/ kT
Ae 1 e e 1
1 1
f FD () / kT
/ kT
Ae 1 e e 1
1
f FD () , A e F / kT
e (F ) / kT 1
AT T=0 K
1
(1) F f FD
1
0 e 1
1
(2) F f FD
0
e 1
∞
0 F F
KT = 1.0 F
0.75
fFD 0.5
F
free electrons in a metal
T=0
T>>0
EF
free electrons in a metal
8 2 Vm3/2
g ()d 3
d
h
(number of electron states)
F
g d
N
0
free electrons in a metal
2 2/3
h 3N N : electron density
F
2m 8V V
Fermi energy
3/2
8 2 Vm 1
n()d 3 (F )/ kT
d
h e 1
(electron energy distribution)
Total internal energy
3
E0 N F
5
3
0 F
5
comparison of the distributions
Maxwell Bose Fermi
Boltzmann Einstein Dirac
e.g. gas molecules e.g. cavity photons (laser) e.g. free electrons in metals
liquid He at low T electrons in white dwarfs
MB: particles 1 2 3
are AB
distinguishable AB
A & B, no AB
restriction on A B
no of particles B A
per state A B
B A
A B
Total 9 distinct
B A
states
1 2 3
BE: particles are
indistinguishable AA Total 6 distinct
A & A, no restriction on no. of states
AA
particles per state
AA
A A
A A
A A
1 / kT
f MB () e e
Bose-Einstein distribution function:
1
f BE () 1 / kT
e e 1
Fermi-Dirac distribution function:
1
f FD () 1 / kT
e e 1
Comparison of the distributions
1
f BE ()
e 1e/ kT 1
f MB () e1e / kT
f()
1 1
f FD ()
e 1e/ kT 1
0
0 1 2 3 4 5
kT
Questions
1. Define microstate, macrostate and ensemble.
7. The Fermi energy of silver is 5.51 eV. (a) what is the average
energy of the free electrons in Silver at 0 K. (b) What is the
speed of the electron corresponding to the above average
energy?