Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Statistical Mechanics
Brian Cowan
Email b.cowan@rhul.ac.uk
Course web pages http://personal.rhul.ac.uk/UHAP/027/PH4211/
You will be redirected here from the MOODLE page
Macrostate
Microstate
• Extensive variables
• Intensive variables
ΔE = ΔQ + ΔW
dE = ∑ Pj dE j + ∑ E j dPj
j j
∑ P dE
j
j j = dW ∑E
j
j dPj = dQ
Shifting energy levels Changing populations of states
Work Heat
P ( E,V , N ) ∝ Ω ( E,V , N )
E1 V1 N1 E2 V2 N2 E1 V1 N 1 E2 V2 N 2
Ω = Ω1 ( E1 ) Ω2 ( E2 )
Ω = Ω1 ( E ) Ω2 ( E0 − E )
Maximise Ω by varying E.
dΩ dΩ1 dΩ2
= Ω2 − Ω1 =0
dE dE dE
1 dΩ1 1 dΩ 2
=
Ω1 dE Ω2 dE
log occurs dlnΩ1 dlnΩ2 dS1 dS2 condition for
= or =
naturally dE dE dE dE equilibrium
4211 Statistical Mechanics Week 1 25
1.3.2 Volume change – Pressure
E1 V1 N1 E2 V2 N2 E1 V1 N 1 E2 V2 N 2
E1 V1 N1 E2 V2 N2 E1 V1 N1 E2 V2 N2
Ω system of interest
fixed diathermal wall energy E
ΩB
P ( E ) ∝ e− E kT
The Boltzmann factor is a key result. Richard Feynman says:
“This fundamental law is the summit of statistical
mechanics, and the entire subject is either a slide-
down from the summit, as the principle is applied to
various cases, or the climb-up to where the
fundamental law is derived and the concepts of
thermal equilibrium and temperature clarified”.
R. P. Feynman, Statistical Mechanics, Benjamin 1972.
4211 Statistical Mechanics Week 1 29
1.3.5 Particle and energy exchange with the rest of the world
– the Gibbs factor
The Grand Canonical Distribution Function
Ω system of interest
fixed diathermal
energy E
permeable wall
particles N
ΩB
P ( E ) ∝ e− E kT
e− E kT
P(E) =
Z
Z = ∑e j
−E kT
system of interest
S = −k ∑ Pj ln Pj
j
= −k ln Pj .
M!
Ω=
n1 !n2 !n3 !…
so the total entropy is
( n1 !n2 !n3 !… )
M!
Stot = k ln .
∑ ∑
nj ln nj +
j j
∑
Now put the first M as nj, then
j
nj
Stot = k( nj ln nj) = − k nj ln( )
∑ ∑ ∑
nj ln M − .
j j j
M
Mean entropy of our particular system is 1/M of this:
nj nj
ln( )
∑M ∑
S=−k =−k Pj ln Pj
j
M j
since Pj = nj /M. = − k ⟨Pj⟩ Gibbs entropy
4211 Statistical Mechanics Week 2 2
1.4.3 Free Energy
− E j ( N ,V ) kT
e
Z ( N ,V , T ) = ∑ e
− E j ( N ,V ) kT
Pj ( N ,V , T ) = ,
Z ( N ,V , T ) j
⎛ Ej ⎞
ln Pj = − ⎜ + ln Z ⎟
⎝ kT ⎠
Ej
S =k + ln Z
kT
E
S = + k ln Z
T
E − TS = −kT ln Z
F = E − TS F = −kT ln Z
4211 Statistical Mechanics Week 1 33
1.4.4 Thermodynamic Variables
A host of thermodynamic variables can be obtained from the
partition function. This is seen from the differential of the free
energy.
dE = TdS − pdV + µ dN
but F = E − TS
so that dF = − SdT − pdV + µ dN
Then we can identify the partial derivatives:
∂F ∂ ln Z
µ= = −kT
∂N T ,V ∂N T ,V
∂ ln Z
and then E = F + TS = kT 2
∂T V , N
★ So all follows from differentiating Z.
4211 Statistical Mechanics Week 1 35