Liouville's Theorem shows that, for conserved classical systems, the local density of microstates following a particle path through phase space is constant as viewed by an observer moving with the ensemble (i.e., the total or convective time derivative is zero). Thus, if the microstates are uniformly distributed in phase space initially, they will remain so at all times. Liouville's theorem ensures that the notion of time average makes sense, but ergodicity does not follow from Liouville's theorem.
In macroscopic systems, the timescales over which a system can truly explore the entirety of its own phase space can be sufficiently large that the thermodynamic equilibrium state exhibits some form of ergodicity breaking. A common example is that of spontaneous magnetisation in ferromagnetic systems, whereby below the Curie temperature the system preferentially adopts a non-zero magnetisation even though the ergodic hypothesis would imply that no net magnetisation should exist by virtue of the system exploring all states whose time-averaged magnetisation should be zero. The fact that macroscopic systems often violate the literal form of the ergodic hypothesis is an example of spontaneous symmetry breaking. However, complex disordered systems such as a spin glass show an even more complicated form of ergodicity breaking where the properties of the thermodynamic equilibrium state seen in practice are much more difficult to predict purely by symmetry arguments.
Statistical mechanics | Philosophy of thermal and statistical physics | Hypotheses
Ergodenhypothese | Hypothèse d'ergodicité | Ergodiciteit | Ergodinen hypoteesi
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"Ergodic hypothesis".
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