Thermodynamics – Microcanonical Ensemble Probability Density Distribution

phase-spaceprobabilitystatistical mechanicsthermodynamics

In microcanonical ensemble the probability density function is postulated as $\rho(q,p)=const.\times\delta(E-E_0)$ so the probability of an ensemble being in an element of phase space $\mathrm{d} q \mathrm{d} p$ is $\mathrm{d} P = \rho(p,q) \mathrm{d} p \mathrm{d} q$. But since $\rho(p,q)$ is constant for a given energy $E_0$ of the ensemble, and we know that for example all gas particles being in one half of a container is highly unlikely but still allowed, does this mean that phase space $\mathrm{d} p \mathrm{d} q$ belonging to a state describing the aforementioned example is much smaller than the phase space belonging to the equilibrium state? Is my conclusion correct? And if it is, can I conclude it in a more rigorous way than pointing out the example?

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Best Answer

There are a few concepts that should be better focused, to formulate this question precisely.

An ensemble of Classical Statistical Mechanics is the set of all possible configurations in phase space, each configuration being characterized by the set of its Hamiltonian coordinates $q=(q_1,q_2,\dots,q_N)$ and $p=(p_1,p_2,\dots,p_N)$. Therefore, there is nothing like the probability of an ensemble being in an element of phase space. Instead, we can safely speak about the probability of a system of the ensemble being in a volume of the phase space. When such a volume is so small that the variations of the probability density over the volume are negligible, we can say that the probability of that microscopic state is ${\mathrm dP}=\rho(q,p){\mathrm dq}{\mathrm dp}$.

If $\rho(q,p)$ is a constant over the hypersurface $H(q,p)=E$ (where $H$ is the Hamiltonian, and $E$ a possible value of the energy), all the subsets of the phase space on such a hypersurface with the same volume ${\mathrm dq}{\mathrm dp}$ have the same probability.

This fact implies that each microstate is as probable as any other. However, a set of microstates may be overwhelming more probable than others. In particular, the collection of microstates such that all the particles occupy only half of the volume has a negligible probability compared to the set where there is almost the same number of particles in the two half-volumes.

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