Chapter 6: Basic Methods & Results of

Statistical Mechanics + Chapter 7: Simple

Applications of Statistical Mechanics
Overview + Details & Applications
 Chapter 6: Basic Methods & Results of
Statistical Mechanics + Chapter 7: Simple
Applications of Statistical Mechanics
Overview + Details & Applications
Subtitle:
Statistical
Mechanics
in the
“Canonical
Ensemble”
Key Concepts In Statistical Mechanics
The Basic Idea (early lectures in this course):
Macroscopic properties are thermal
averages of microscopic properties.
Key Concepts In Statistical Mechanics
The Basic Idea (early lectures in this course):
Macroscopic properties are thermal
averages of microscopic properties.
• First, replace the system with a set of a large
number of systems "identical" to the first &
average over all of the systems. We call the set of
systems
“The Statistical Ensemble”.
Key Concepts In Statistical Mechanics
The Basic Idea (early lectures in this course):
Macroscopic properties are thermal
averages of microscopic properties.
• First, replace the system with a set of a large number
of systems "identical" to the first & average over all
of the systems. We call the set of systems
“The Statistical Ensemble”.
• “Identical Systems” means that they are all in
the same thermodynamic macrostate. To do
calculations we have to first
Choose an Ensemble!
 First,
What in the world
does the term
“Canonical”
mean?
Some Science Definitions of
“Canonical”:
 Some Science Definitions of
“Canonical”:
1. Accepted as being Accurate &
Authoritative
 Some Science Definitions of
“Canonical”:
1. Accepted as being Accurate &
Authoritative
2. According to Rules or
Scientific Laws
 Some Science Definitions of
“Canonical”:
1. Accepted as being Accurate &
Authoritative
2. According to Rules or
Scientific Laws
3. Of or Relating to a General
Rule or Standard
Formula
• There are also religious meanings
of “Canonical”:
1. According to or Ordered by
Canon Law
2. The Canonical Rites of the
Catholic Church
3. The Canonical Gospels of
the New Testament.
3 Common Statistical Ensembles:
 3 Common Statistical Ensembles:
1. Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens!  Not Interesting!
 3 Common Statistical Ensembles:
1. Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens!  Not Interesting!
2. The Canonical Ensemble:
Systems with a fixed number N of molecules
in equilibrium with a Heat Reservoir (Heat Bath).
 3 Common Statistical Ensembles:
1. Micro-Canonical Ensemble:
Isolated Systems: Constant Energy E.
Nothing happens!  Not Interesting!
2. The Canonical Ensemble:
Systems with a fixed number N of molecules
in equilibrium with a Heat Reservoir (Heat Bath).
3. The Grand Canonical Ensemble:
Systems in equilibrium with a Heat Bath
which is also a Source of Molecules.
Their chemical potential is fixed.
Example: If Systems of Interest are Gases
Example: If Systems of Interest are Gases
Microcanonical Ensemble
E, V, N fixed, S = kB lnΩ(E,V,N)
Ω(E,V,N)  # Accessible States
 Example: If Systems of Interest are Gases
Microcanonical Ensemble
E, V, N fixed, S = kB lnΩ(E,V,N)
Ω(E,V,N)  # Accessible States
Canonical Ensemble
T, V, N fixed, F = -kBT lnZ(T,V,N)
Z(T,V,N)  Partition Function
 Example: If Systems of Interest are Gases
Microcanonical Ensemble
E, V, N fixed, S = kB lnΩ(E,V,N)
Ω(E,V,N)  # Accessible States
Canonical Ensemble
T, V, N fixed, F = -kBT lnZ(T,V,N)
Z(T,V,N)  Partition Function
Grand Canonical Ensemble
T, V,  fixed,  = -kBTln (T,V,)
(T,V,)  Grand Partition Function
 All Thermodynamic Properties Can Be
Calculated With Any Ensemble
• So, it is up to the problem solver which ensemble is
used. So, we should choose the most convenient
one for a particular problem
• Note that, Historically, the first systems people
applied Statistical Mechanics to were gases.
• It is much more general than that, but when
introducing the theory, many books, including
Reif’s, still focus on gases at first & some of the
first examples discussed are applications to
gases.
All Thermodynamic Properties Can Be
Calculated With Any Ensemble
1. For Gases: PVT properties usually use
The “Canonical Ensemble”
All Thermodynamic Properties Can Be
Calculated With Any Ensemble
1. For Gases: PVT properties usually use
The “Canonical Ensemble”
2. Systems which Exchange Particles:
Such as Vapor-Liquid Equilibrium
use
The Grand Canonical
Ensemble
 Properties of The Canonical & Grand
Canonical Ensembles
• J. Willard Gibbs was the first to show that
An Ensemble Average is Equal to a
Thermodynamic Average:
 Properties of The Canonical & Grand
Canonical Ensembles
• J. Willard Gibbs was the first to show that
An Ensemble Average is Equal to a
Thermodynamic Average:
• That is, for a given property A,
The Thermodynamic Average
can be formally expressed as:
A  nAnPn
 Properties of The Canonical & Grand
Canonical Ensembles
• J. Willard Gibbs was the first to show that
An Ensemble Average is Equal to a
Thermodynamic Average:
• That is, for a given property A,
The Thermodynamic Average
can be formally expressed as:
A  nAnPn
An  Value of F in state (configuration) n
Pn  Probability of the system being in
state (configuration) n.
Canonical Ensemble Probabilities
U n
g ne N
Qcanon   g ne U n
pn  N
Qcanon n
QNcanon  “Canonical Partition Function”
Often called simply the “Partition Function”
gn  Degeneracy of state n

•Note: Un  En  n = Quantum Energy of state n

•Also, most texts use the notation
“Z” for the partition function!
Grand Canonical Ensemble Probabilities :
E n E n
g ne Qgrand   g ne
pn  n
Qgrand
E n  U n  N n
Qgrand  “Grand Canonical Partition Function”
Often called simply the
“Grand Partition Function”
gn  Degeneracy of state n, μ  “Chemical Potential”

Note that most texts use the notation

“ZG” for the Grand Partition Function!
 Partition Functions
• We’ll show that if the volume V, (or other
external parameter) the temperature T, & the
energy levels En (from some microscopic model) of a
system are known, in principle
The Partition Function Z
can be calculated.
 Partition Functions
• We’ll show that if the volume V, (or other
external parameter) the temperature T, & the
energy levels En (from some microscopic model) of a
system are known, in principle
The Partition Function Z
can be calculated.
• We’ll also show that if the partition function Z
is known, it can be used to
Calculate all Thermodynamic
Properties of the System!!.
 Partition Functions
• If the partition function Z is known,
it can be used to Calculate
All Thermodynamic Properties.
 Partition Functions
• If the partition function Z is known,
it can be used to Calculate
All Thermodynamic Properties.
• So, in this way,
Statistical Mechanics is a direct link
between Microscopic Quantum
Mechanics & Classical
Macroscopic Thermodynamics.
 Canonical Ensemble Partition
Function Z
• Starting from the fundamental postulate of equal
a priori probabilities, the following are obtained:
 Canonical Ensemble Partition
Function Z
• Starting from the fundamental postulate of equal
a priori probabilities, the following are obtained:
• ALL RESULTS of Classical Thermodynamics,
plus their statistical underpinnings;
 Canonical Ensemble Partition
Function Z
• Starting from the fundamental postulate of equal
a priori probabilities, the following are obtained:
• ALL RESULTS of Classical Thermodynamics,
plus their statistical underpinnings;
• A MEANS OF CALCULATING the
thermodynamic variables (E, H, F, G, S)
from a single statistical parameter, the partition
function Z (or Q), which may be obtained from
the energy-levels of a quantum system.
 Canonical Partition Function Z
• The Partition Function Z is
A MEANS OF CALCULATING
all thermodynamic variables
(E, H, F, G, S)
• Z is obtained from the energy-levels of a quantum
system. For a quantum system in equilibrium
with a heat reservoir, Z is defined as:
Z  i exp(-εi/kBT)
εi is the energy of the i’th quantum state.
 The Partition Function for a Quantum
System in Contact with a Heat Reservoir:
, /k T)
Z  i exp(-ε i B
εi = Energy of the i’th state.
• The connection to the macroscopic entropy
function S is through the microscopic parameter
Ω, which, as we already know, is the number of
microstates in a given macrostate.
• The connection between them, as discussed in
previous chapters, is
S = kBln Ω. 36
Relationship of Z to Macroscopic Parameters
Relationship of Z to Macroscopic Parameters
Summary:
Canonical Ensemble Partition Function Z:
(Derivation for Ē on the board.
Other derivations are in the book!)
• Internal Energy: Ē  E = - ∂(lnZ)/∂β
Relationship of Z to Macroscopic Parameters
Summary:
Canonical Ensemble Partition Function Z:
(Derivation for Ē on the board.
Other derivations are in the book!)
• Internal Energy: Ē  E = - ∂(lnZ)/∂β
rms Energy Fluctuations:
<(ΔE)2> = [∂2(lnZ)/∂β2]
β = 1/(kBT), kB = Boltzmann’s constantt.
Relationship of Z to Macroscopic Parameters
Summary:
Canonical Ensemble Partition Function Z:
(Derivation for Ē on the board.
Other derivations are in the book!)
• Internal Energy: Ē  E = - ∂(lnZ)/∂β
rms Energy Fluctuations:
<(ΔE)2> = [∂2(lnZ)/∂β2]
β = 1/(kBT), kB = Boltzmann’s constantt.
• Entropy: S = kB[βĒ + lnZ]
An important, frequently used result!
 Canonical Ensemble Partition Function Z:
(Derivations are in the book!)
• Helmholtz Free Energy:
F = E – TS = – (kBT)lnZ
 Canonical Ensemble Partition Function Z:
(Derivations are in the book!)
• Helmholtz Free Energy:
F = E – TS = – (kBT)lnZ
Note that this gives: Z = exp[-F/(kBT)]
dF = S dT – PdV, so
S = – (∂F/∂T)V, P = – (∂F/∂V)T
 Canonical Ensemble Partition Function Z:
(Derivations are in the book!)
• Helmholtz Free Energy:
F = E – TS = – (kBT)lnZ
Note that this gives: Z = exp[-F/(kBT)]
dF = S dT – PdV, so
S = – (∂F/∂T)V, P = – (∂F/∂V)T
• Gibbs Free Energy:
G = F + PV = PV – kBT lnZ.
 Canonical Ensemble Partition Function Z:
(Derivations are in the book!)
• Helmholtz Free Energy:
F = E – TS = – (kBT)lnZ
Note that this gives: Z = exp[-F/(kBT)]
dF = S dT – PdV, so
S = – (∂F/∂T)V, P = – (∂F/∂V)T
• Gibbs Free Energy:
G = F + PV = PV – kBT lnZ.
• Enthalpy:
H = E + PV = PV – ∂(lnZ)/∂β
 Canonical Ensemble:
Heat Capacity & Other Properties
• Partition Function:
Z = nexp(-En),  = 1/(kBT)
 Canonical Ensemble:
Heat Capacity & Other Properties
• Partition Function:
Z = nexp(-En),  = 1/(kBT)
• Mean Energy:
Ē = – (lnZ)/ = - (1/Z)Z/
 Canonical Ensemble:
Heat Capacity & Other Properties
• Partition Function:
Z = nexp(-En),  = 1/(kBT)
• Mean Energy:
Ē = – (lnZ)/ = - (1/Z)Z/
• Mean Squared Energy:
E2 = rprEr2/rpr = (1/Z)2Z/2.
 Canonical Ensemble:
Heat Capacity & Other Properties
• Partition Function:
Z = nexp(-En),  = 1/(kBT)
• Mean Energy:
Ē = – (lnZ)/ = - (1/Z)Z/
• Mean Squared Energy:
E2 = rprEr2/rpr = (1/Z)2Z/2.
• nth Moment:
n n n n n
E  = rprEr /rpr = (-1) (1/Z)  Z/
 Canonical Ensemble:
Heat Capacity & Other Properties
• Partition Function:
Z = nexp(-En),  = 1/(kBT)
• Mean Energy:
Ē = – (lnZ)/ = - (1/Z)Z/
• Mean Squared Energy:
E2 = rprEr2/rpr = (1/Z)2Z/2.
• nth Moment:
n n n n n
E  = rprEr /rpr = (-1) (1/Z)  Z/
• Mean Square Deviation:
(ΔE)2 = E2 - (Ē)2 = 2lnZ/2 = - Ē/ .
 Canonical Ensemble:
Constant Volume Heat Capacity
CV = (Ē/T)V = (Ē/)(d/dT) = - k2Ē/
 Canonical Ensemble:
Constant Volume Heat Capacity
CV = (Ē/T)V = (Ē/)(d/dT) = - k2Ē/
using results for the Mean Square Deviation:
(ΔE)2 = E2 - (Ē)2 = 2lnZ/2 = - Ē/
 Canonical Ensemble:
Constant Volume Heat Capacity
CV = (Ē/T)V = (Ē/)(d/dT) = - k2Ē/
using results for the Mean Square Deviation:
(ΔE)2 = E2 - (Ē)2 = 2lnZ/2 = - Ē/
CV can thus be re-written as:
CV = k2(ΔE)2 = (ΔE)2/kBT2
 Canonical Ensemble:
Constant Volume Heat Capacity
CV = (Ē/T)V = (Ē/)(d/dT) = - k2Ē/
using results for the Mean Square Deviation:
(ΔE)2 = E2 - (Ē)2 = 2lnZ/2 = - Ē/
CV can be re-written as:
CV = k2(ΔE)2 = (ΔE)2/kBT2
so that:
(ΔE)2 = kBT2CV
 Canonical Ensemble:
Constant Volume Heat Capacity
CV = (Ē/T)V = (Ē/)(d/dT) = - k2Ē/
using results for the
Mean Square Deviation:
(ΔE)2 = E2 - (Ē)2 = 2lnZ/2 = - Ē/
CV can be re-written as:
CV = k2(ΔE)2 = (ΔE)2/kBT2
so that:
(ΔE)2 = kBT2CV
Note that, since (ΔE)2 ≥ 0
(i) CV ≥ 0 & (ii) Ē/T ≥ 0.
 Ensembles in Classical Statistical
Mechanics
• We’ve seen that, for a classical description, it is
convenient to use a classical phase space for a system
with f degrees of freedom. That is, use f generalized
coordinates & f generalized momenta (qi,pi).
• The classical mechanics problem is done in the
Hamiltonian formulation with a Hamiltonian
energy function H(q,p).
• There may also be a few constants of motion:
energy, particle number, volume, ...
 The Canonical Distribution in
Classical Statistical Mechanics
The Partition Function
has the form:
Z ≡ ∫∫∫d3r1d3r2…d3rN d3p1d3p2…d3pN e(-E/kT)
 The Canonical Distribution in
Classical Statistical Mechanics
The Partition Function
has the form:
Z ≡ ∫∫∫d3r1d3r2…d3rN d3p1d3p2…d3pN e(-E/kT)
A 6N Dimensional Integral!
 The Canonical Distribution in
Classical Statistical Mechanics
The Partition Function
has the form:
Z ≡ ∫∫∫d3r1d3r2…d3rN d3p1d3p2…d3pN e(-E/kT)
A 6N Dimensional Integral!
• This assumes that we have already solved the
classical mechanics problem for each particle in the
system so that we know the total energy E for the N
particles as a function of all positions ri & momenta pi.
E  E(r1,r2,r3,…rN,p1,p2,p3,…pN)
CLASSICAL Statistical Mechanics:
• Let A ≡ any measurable, macroscopic
quantity. The thermodynamic average
of A ≡ <A>. This is what is measured.
CLASSICAL Statistical Mechanics:
• Let A ≡ any measurable, macroscopic
quantity. The thermodynamic average
of A ≡ <A>. This is what is measured.
• Use probability theory to calculate <A> :
P(E) ≡ e [-E/(k T)]
B /Z
CLASSICAL Statistical Mechanics:
• Let A ≡ any measurable, macroscopic
quantity. The thermodynamic average
of A ≡ <A>. This is what is measured.
• Use probability theory to calculate <A> :
P(E) ≡ e [-E/(k T)]
B /Z
<A>≡ ∫∫∫(A)d3r1d3r2…d3rN d3p1d3p2…d3pNP(E)
Another 6N Dimensional
Integral!
Now, two slides from the
first class day!
A quote from Richard
Feynman:
 Statistical Mechanics
(Classical or Quantum)
P(E), Z

Calculation of
Measurable
Equations of
Quantities
Motion

The Statistical/Thermal
Physics “Mountain”
 P(E), Z
Calculation of
Equations of Measurable
Motion Quantities

Statistical/Thermal Physics “Mountain”

•The entire subject is either the “climb” UP to the summit
(calculation of P(E), Z) or the slide DOWN (use of P(E), Z
to calculate measurable properties).
•On the way UP: Thermal Equilibrium & Temperature
are defined from statistics. On the way DOWN, all of
Thermodynamics can be derived, beginning with
microscopic theory.
•We are now near the peak of this mountain!