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Statistical Mechanics

Manual: General · Subject: Statistical Mechanics

Entropy, partition functions, and thermodynamic distributions

Bridging Microscopic and Macroscopic

Microstates and the Boltzmann Definition of Entropy

For a system with Ω\Omega accessible microstates, Boltzmann's entropy: S=kBln⁡ΩS = k_B \ln \Omega In the canonical ensemble (fixed TT, VV, NN), the probability of microstate ii with energy EiE_i:<br>Pi=e−Ei/kBTZ,Z=∑ie−Ei/kBTP_i = \frac{e^{-E_i / k_B T}}{Z}, \quad Z = \sum_i e^{-E_i / k_B T} ZZ is the partition function.

Thermodynamic Quantities from Z

All thermodynamic quantities follow from ZZ:

  • Free energy: F=−kBTln⁡ZF = -k_BT \ln Z
  • Average energy: ⟨E⟩=−∂ln⁡Z/∂β\langle E \rangle = -\partial \ln Z / \partial \beta where β=1/kBT\beta = 1/k_BT
  • Entropy: S=kB(ln⁡Z+β⟨E⟩)S = k_B(\ln Z + \beta \langle E \rangle)
  • Heat capacity: CV=−kBβ2∂2ln⁡Z/∂β2C_V = -k_B\beta^2 \partial^2 \ln Z / \partial \beta^2
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Quantum Statistics

Bosons obey Bose-Einstein statistics (photons, phonons) and can occupy the same state. Fermions obey Fermi-Dirac statistics (electrons) — no two in the same quantum state (Pauli exclusion). Classical limit: Maxwell-Boltzmann.

In the canonical ensemble, temperature TT is:

The partition function Z=∑ie−βEiZ = \sum_i e^{-\beta E_i} for a two-level system (E=0E = 0 and E=εE = \varepsilon) is:

Write the Fermi-Dirac distribution and explain what it describes.