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Statistical Mechanics and Thermodynamics from Microscopic Laws

Manual: General · Subject: Theoretical Physics

Connect microscopic states to macroscopic temperature, entropy, and ensembles.

From Many Particles to Macroscopic Behavior

Microstates and Macrostates

A macrostate is specified by bulk variables such as energy, pressure, and volume, while a microstate specifies the complete microscopic configuration. Entropy measures the number of compatible microstates, often written as S=kBln⁡ΩS=k_B\ln\Omega.

Ensembles

Different ensembles model different physical situations. The microcanonical ensemble describes isolated systems with fixed energy, the canonical ensemble describes systems in thermal contact with a heat bath, and the grand canonical ensemble allows exchange of particles as well as energy.

Partition Function

In the canonical ensemble, the partition function is Z=∑ie−βEi,β=1/(kBT).Z=\sum_i e^{-\beta E_i}, \qquad \beta=1/(k_B T). Once ZZ is known, thermodynamic quantities can be derived by differentiation, making it a generating function for equilibrium physics.

Thermodynamic Relations

The free energy is F=−kBTln⁡ZF=-k_B T\ln Z. From it one can obtain entropy, internal energy, and response functions. This makes equilibrium thermodynamics a compact macroscopic summary of microscopic probability.

What does the partition function do in the canonical ensemble?

What is entropy in statistical mechanics?

Ensemble Comparison

EnsembleFixed quantities
MicrocanonicalEE, NN, VV
CanonicalTT, NN, VV
Grand canonicalTT, μ\mu, VV