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Slides 1
Statistical Mechanics
Brian Cowan
Email b.cowan@rhul.ac.uk
Course web pages h7p://personal.rhul.ac.uk/UHAP/027/PH4211/
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Macrostate
Microstate
• Extensive variables
• Intensive variables
ΔE = ΔQ + ΔW
E = ∑ Pj E j
j
dE = ∑ Pj dE j + ∑ E j dPj
j j
∑ P dE
j
j j = dW ∑Ej
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 subject to varying E.
dΩ dΩ1 dΩ2
= Ω2 − Ω1 =0
dE dE dE
1 dΩ1 1 dΩ 2
=
Ω1 dE Ω2 dE
dlnΩ1 dlnΩ2 dS1 dS2
= or =
dE dE dE dE
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 .
⎛ 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