Thermal Physics Lecture Notes

Based on Schroeder's "An Introduction to Thermal Physics"

1. The Two-State Paramagnet

Paramagnet Definition: A material whose magnetic dipoles align parallel to an externally applied
magnetic field.

Two-State System: Each magnetic dipole can have only two possible orientations:
Parallel to the external field (lower energy)

Antiparallel to the external field (higher energy)

Magnetic Dipole Sources:

Individual electrons (unpaired)

Groups of electrons in atoms

Atomic nuclei

Key Parameters:
N₁: Number of dipoles pointing up
N₂: Number of dipoles pointing down

N = N₁ + N₂: Total number of dipoles

Macrostate: Defined solely by the values of N₁ and N₂

Each macrostate has a multiplicity (number of ways to achieve that distribution)
Multiplicity formula: Ω(N₁) = N!/(N₁!N₂!) = N!/[N₁!(N-N₁)!]

External Field Effects:

Applied magnetic field exerts torque on dipoles
Field tries to align dipoles in parallel orientation (lower energy state)

System's energy depends on the total number of up vs. down dipoles

2. The Einstein Model of a Solid

Basic Concept: Models a solid as a collection of independent quantum oscillators

Key Characteristics:
Equal-sized energy units for quantum mechanical harmonic oscillators
Each quantum oscillator can only hold energy in discrete "units"

Energy unit defined as ℏω = h/2π × f (where h is Planck's constant and f is oscillator frequency)

Oscillator Arrangement:
3D solid contains N atoms
 Each atom can oscillate in three independent directions
Total of 3N oscillators in the system

Energy States:
Each oscillator can exist in various energy states (0, 1, 2, 3, etc.)

Energy states increase in integer multiples of ℏω

The system's total energy depends on the distribution of energy across all oscillators

Microstates:
Each specific configuration of energy across all oscillators is a microstate
Example with 3 oscillators: microstate notation (n₁,n₂,n₃) shows energy units per oscillator

Microstates can be represented graphically with dots and dashes

Multiplicity Formula:
Ω(N,q) = (q+N-1)!/[q!(N-1)!]

Where N = number of oscillators and q = number of energy units

Visualization:
Microstates can be represented using dots (●) for oscillators and dashes (-) for energy units
Example: ●●●-- represents a system with 3 oscillators and 2 energy units

This notation allows unique representation of any microstate

3. Interacting Systems
Composite Systems: Two or more systems that can exchange energy with each other but are
isolated from the rest of the universe
Example: Two Einstein solids A and B that can share energy

Macrostate of Composite System: Defined by the energies UA and UB of each subsystem

For weakly coupled systems, energy exchange between solids is much slower than energy
exchange within each solid

Total Multiplicity: When two systems can exchange energy, the total multiplicity is the product of
individual multiplicities:
Ωtotal = ΩA × ΩB

This is because systems are independent of each other

Example with Small Systems:

Two solids A and B, each with 3 oscillators

Total energy of 6 units (qtotal = qA + qB = 6)

7 possible macrostates (qA = 0, 1, 2, 3, 4, 5, 6)

Total number of microstates = 462 = (6+6-1)!/(6!(6-1)!)

 Fundamental Assumption of Statistical Mechanics:
Over long time scales, all accessible microstates are equally probable

Some macrostates are more probable than others because they contain more microstates

Example: Macrostate with qA = 3 (and qB = 3) has multiplicity of 100, making it ~3.6 times more
likely than macrostate with qA = 0 (multiplicity of 28)

Larger Systems Example:

System A: 300 oscillators

System B: 200 oscillators

Total energy: 100 units

101 possible macrostates

Most likely macrostate has qA = 60, with multiplicity of 7 × 10¹⁴⁴

Least likely macrostate is ~10⁸³ times less probable than the most likely one

Total number of microstates: 9 × 10¹⁴⁸

Irreversible Behavior:
If a system starts far from the most probable state (e.g., qA << 60), energy will spontaneously
flow until it reaches the most likely macrostate

This explains the physical basis of heat flow - a probabilistic phenomenon

Energy flows spontaneously from B to A but not from A to B (aside from minor fluctuations)

Second Law of Thermodynamics:

The "law of increase of multiplicity" is one version of the second law

Systems spontaneously evolve toward states of higher multiplicity

The most likely macrostate has the greatest multiplicity

This isn't a fundamental law but a strong statistical statement

4. Stirling's Approximation
Purpose: A mathematical tool for evaluating factorials of large numbers, essential for multiplicity
calculations in large systems
Formula:
N! ≈ (N/e)ᴺ√(2πN) (Equation 2.14)
This is accurate in the limit where N ≫ 1

Derivation Logic:
N! is the product of N factors from 1 to N

Crude approximation: N! ≈ Nᴺ (overestimate)

Better approximation: N! ≈ (N/e)ᴺ = Nᴺeᵏᴺ

 Full Stirling's approximation adds correction factor √(2πN)

Logarithmic Form:
ln(N!) ≈ N ln(N) - N (Equation 2.16)
More convenient for very large numbers

Quite accurate for N ≥ 100

Accuracy:
For N = 10: Error ≈ 0.83%

For N = 100: Error ≈ 0.83%

Becomes increasingly accurate as N increases

5. Multiplicity of Large Einstein Solids

High-Temperature Limit (q ≫ N):
Starting with exact formula: Ω(N,q) = (q+N-1)!/(q!(N-1)!)

Approximation: (q+N)! ≈ (q+N)⁽ᑫ⁺ᴺ⁾e⁻⁽ᑫ⁺ᴺ⁾√(2π(q+N))

Taking logarithm and applying Stirling's approximation:

ln Ω ≈ (q+N)ln(q+N) - q ln q - N ln N

For q ≫ N: ln(q+N) ≈ ln q + N/q

Final result: Ω(N,q) ≈ eᴺ⁽ᶦⁿ⁽ᑫ/ᴺ⁾⁺¹⁾ = (e·q/N)ᴺ

Low-Temperature Limit (q ≪ N):

Formula similar to high-temperature case but different

Approximately: Ω(N,q) ≈ (q+N-1)!/(q!(N-1)!) ≈ ((q+N)/q)ᑫ((q+N)/N)ᴺ/√(2πq(q+N)/N)

Two-State Paramagnet Comparison:

Using Stirling's approximation, the multiplicity formula for a paramagnet simplifies to Ω ≈
(N₁/N)ᴺ¹(N₂/N)ᴺ²

In the limits considered, Einstein solids and paramagnets show similar statistical behavior

6. Sharpness of the Multiplicity Function

Sharp Peak in Probability Distribution:
For two large interacting Einstein solids with total energy q ≫ N

Combined system multiplicity: Ω = (e·qₐ/N)ᴺ(e·qᵦ/N)ᴺ = (e/N)²ᴺ(qₐqᵦ)ᴺ

Graph of Ω vs. qₐ shows extremely sharp peak at qₐ = q/2

At peak (equal energy distribution): Ωmax = (e/N)²ᴺ(q/2)²ᴺ

Gaussian Distribution Near Peak:

Setting qₐ = q/2 + x and qᵦ = q/2 - x
Multiplicity near peak: Ω = Ωmax·e⁻ᴺ⁽²ˣ/ᑫ⁾²
 Falls to 1/e of maximum when x = q/(2√N)
Width of peak is extremely narrow compared to full scale

For N = 10²⁰, width is only one part in ten billion of the graph's scale

Extreme Narrowness of Peak:

If width of peak is 1 cm, full scale would stretch 100,000 km (more than twice Earth's
circumference)

At x = 10·q/(2√N), multiplicity is less than 10⁻⁴⁴ of maximum

Physical Implications:
Random fluctuations away from equal distribution are utterly unmeasurable

To measure energy changes would require precision to ten significant figures

Once in thermal equilibrium, system is essentially always in its most likely macrostate

As system size approaches infinity, fluctuations become vanishingly small (thermodynamic limit)

Important Concepts to Remember

1. Statistical Nature: Both models illustrate how macroscopic properties emerge from microscopic
states

2. Multiplicity: The number of ways to arrange a system is crucial for thermodynamic calculations

3. Quantization: Energy exists in discrete units, not continuously

4. Spontaneous Processes: Systems naturally evolve toward states with greater multiplicity

5. Irreversibility: The statistical tendency toward higher-multiplicity states explains the direction of
natural processes

6. Probability vs. Certainty: Thermodynamic laws are extremely likely but not absolutely certain

7. Stirling's Approximation: Essential mathematical tool for handling large factorial calculations

8. Thermodynamic Limit: As systems grow larger, probability distributions become extremely sharp

9. Most Likely Macrostate: For large systems, the most likely state dominates completely

10. Mathematical Foundation: Statistical mechanics provides the mathematical basis for
thermodynamic laws