Statistical Mechanics and Thermodynamics from Microscopic Laws
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 .
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 Once is known, thermodynamic quantities can be derived by differentiation, making it a generating function for equilibrium physics.
Thermodynamic Relations
The free energy is . 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?
The partition function encodes Boltzmann weights for all accessible states.
Correct answer: It summarizes all equilibrium statistical weights
What is entropy in statistical mechanics?
Higher entropy generally means more accessible microstates.
Correct answer: A measure of the number of microscopic configurations compatible with a macrostate.
Ensemble Comparison
| Ensemble | Fixed quantities |
|---|---|
| Microcanonical | , , |
| Canonical | , , |
| Grand canonical | , , |