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Published online by Cambridge University Press: 09 June 2025
For a system in contact with a heat bath, it is shown how the distribution of any observable follows from a microcanonical description for the isolated system consisting of the system of interest and heat bath. The weak coupling approximation then leads to the standard expression for the canonical distribution. Free energy, canonical entropy, and pressure are introduced. For large systems, the equivalence of this canonical description with the microcanonical one is shown. For systems in contact with a particle reservoir, the grand-canonical distribution is derived. If the weak coupling approximation does not hold, the corrections due to strong coupling are determined. In particular, internal energy, free energy ,and entropy are identified such that the usual relations for these thermodynamic potentials hold true even in strong coupling.
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