[Physics] Why is the fundamental postulate of statistical mechanics true

statistical mechanics

As I'm sure folks here know, the principle of equal a priori probabilities, sometimes called the fundamental postulate of statistical mechanics, states the following:

For an isolated system with an exactly known energy and exactly known composition, the system can be found with equal probability in any microstate consistent with that knowledge.

This isn't sitting right in my head because I also know that particles want to occupy the lowest possible energy.

How can it be that all microstates (consistent with the given macrostate – i.e., number of particles N, total volume V, and total energy E) have equal probability, when we know that particles want to occupy lower-energy states? Wouldn't the microstates which have more particles distributed in lower-energy states have a higher probability?

The principle of equal a priori probabilities implies to me that if we had a total energy of E = 100 J and N = 10 particles, it's equally likely to have

  • 10 particles all with 10 J of energy or
  • 9 particles with 1 J of energy each and 1 particle with 91 J of energy.

Whereas, to me, the second one seems intuitively far more unlikely! But each of these microstates is consistent with the overall macrostate. And the macrostate makes no statement regarding the specific energies of each particle. How do we reconcile the principle of equal a priori probabilities with the fact that particles want to assume the lowest possible energy states?

Best Answer

The "search" for lowest energy states is a transient effect. If a system is in a high energy state and can emit energy out of the system, it will do so until the energy of the system diminishes to where it is no longer energetically favorable to do so.

This "isolated system" deals with the steady state case, where energy is not entering or leaving for an arbitrarily long time. Steady state systems exhibit different behaviors than transients.

Given two microstates A and B, we know that the probability of a A->B transition occurring must be the same as the probability of B->A because both states have equal energy. It's easy to see that if the probability of those transitions are equal, then the transient case would have smoothed them out before we arrived at steady state. If P(A) < P(B), we would expect more B->A transitions than A->B transitions, by Bayes' theorem, until eventually we reach P(A) = P(B).

Worth noting however: postulates are not provable. It's called the fundamental postulate of statistical mechanics because we can't actually prove that systems will do this. However, all systems yet observed do indeed demonstrate this behavior, even systems that were designed to break it. You could, however, turn it around and say that if the micro-states are not equiprobable, then you by definition do not fully know the composition of the system.

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