1. Introduction to Statistical & Thermal Physics (+ Some Definitions)

2. Basic Definitions & Terminology
Thermodynamics (“Thermo”)
is a macroscopic theory!
Thermo ≡ The study of the Macroscopic properties of systems based on a few laws & hypotheses. It results in
The Laws of Thermodynamics!

3. Thermodynamics (“Thermo”)
1. Derives relations between the macroscopic, measureable properties (& parameters) of a system (heat capacity, temperature, volume, pressure, ..).
2. Makes NO direct reference to the microscopic structure of matter.

4. Thermo: Makes NO direct reference to the microscopic structure of matter.
For example, from thermo, we can derive that, for an ideal gas, the heat capacities (per mole) are related by
Cp– Cv = R.
But, thermo gives no prescription for calculating numerical values for Cp, Cv.
Calculating these requires a microscopic model & statistical mechanics.

5. Kinetic Theory is a microscopic theory!
(Boltzmann, Maxwell & others in the 19th Century)
1. It applies the Laws of Mechanics (Classical or Quantum) to a microscopic model of the individual molecules of a system.
2. It allows the calculation of various Macroscopically measurable quantities on the basis of a Microscopic theory applied to a model of the system.
For example, it might be able to calculate the specific heat
Cv using Newton’s 2nd Law along with known force laws
between particles that make up the substance of interest.

6. Kinetic Theory is a microscopic theory!
3. It uses the microscopic equations of motion for individual particles.
4. It uses the methods of Probability & Statistics & the equations of motion of the particles to calculate the (thermal average) Macroscopic properties of a substance.

7. Statistical Mechanics (or Statistical Thermodynamics)
1. Ignores a detailed consideration of molecules as individuals.
2. Is a Microscopic, Statistical approach to calculation of Macroscopic quantities.
3. Applies the methods of Probability & Statistics to Macroscopic systems with HUGE numbers of particles.

8. Statistical Mechanics
3. For systems with known energy
(Classical or Quantum) it gives
BOTH
A. Relations between Macroscopic quantities (like Thermo)
AND
B. NUMERICAL VALUES of
them (like Kinetic Theory).

9. This course covers all three! Statistical Mechanics:
1. Thermodynamics
2. Kinetic Theory
3. Statistical Mechanics
Statistical Mechanics:
Reproduces ALL of Thermodynamics & ALL of Kinetic Theory.
It is more general than either!

10. A Hierarchy of Theories Statistical Mechanics
(of Systems with a Huge Number of Particles)
Statistical Mechanics
(the most general theory)
___________|__________
| |
Thermodynamics Kinetic Theory
(a general, macroscopic theory) (a microscopic theory most
easily applicable to gases)

11. Some Remarks on Statistical & Thermal Physics
A brief overview of Statistical Mechanics. A general overview. No worry about
details now! (We’ll derive them later!)
The Key Principle of CLASSICAL
Statistical Mechanics is as follows:

12. The Key Principle of CLASSICAL Statistical Mechanics is as follows:
Consider a system with N particles (N ~ 1024) with 3d positions r1,r2,r3,…rN, & momenta
p1,p2,…pN. The system is in Thermal Equilibrium at absolute temperature T. We’ll show that the probability of the system having energy E is:
P(E) ≡ e[-E/(kT)]/Z
Z ≡ “Partition Function”
T ≡ Absolute Temperature,
k ≡ Boltzmann’s Constant
Note: The Canonical
Ensemble is assumed!!

13.  A 6N Dimensional Integral!
The Classsical Partition Function
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)
We’ll derive & discuss this later!

14. CLASSICAL Statistical Mechanics: P(E) ≡ e[-E/(kT)]/Z
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/(kT)]/Z
<A>≡ ∫∫∫(A)d3r1d3r2…d3rN d3p1d3p2…d3pNP(E)
 Another 6N Dimensional Integral!
We’ll derive & discuss this later!

15. Statistical Mechanics is: The Canonical Ensemble
The Key Principle of QUANTUM
Statistical Mechanics is:
Consider a system which can be in any one of N quantum states (N ~ 1024). The system is in Thermal Equilibrium at absolute temperature T. We’ll show that the probability of the system being in state j with energy Ej is:
The Canonical Ensemble
is assumed!!
Z ≡ “Partition Function”
T ≡ Absolute Temperature
k ≡ Boltzmann’s Constant

16. The Quantum Mechanical
Partition Function
Z ≡ ∑jexp[-Ej/(kT)]
We’ll derive & discuss this later!

17. QUANTUM 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>.
<A> ≡ ∑j <j|A|j>Pj l
<j|A|j> ≡ Quantum Mechanical expectation value of A in quantum state j.
We’ll derive & discuss this later!

18. Quoting Richard P. Feynman*: “P(E) & Z are at the summit of both
The point of showing this now is that Classical & Quantum Statistical Mechanics both revolve around the calculation of P(E) or P(En).
To calculate the probability distribution, we need to calculate the Partition Function Z (similar in the classical & quantum cases).
Quoting Richard P. Feynman*:
“P(E) & Z are at the summit of both
Classical & Quantum
Statistical Mechanics.”
* From “Statistical Mechanics”
by R.P. Feynman, (W.A. Benjamin, 1972)

19. P(E), Z The Statistical/Thermal Physics “Mountain”
Statistical Mechanics
(Classical or Quantum)
P(E), Z
Calculation of
Measurable
Quantities
Equations of
Motion
The Statistical/Thermal Physics “Mountain”

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