Saturday, May 25, 2019

statistical mechanics - Deriving Boltzmann statistics from the maximum entropy principle


In some lecture notes I have, the author derives the expectation value of the occupation numbers for a discrete system of fermions as follows:


Consider all states that have a certain energy εs. There shall be as such states, and ns particles occupying these states. Then, the number of configurations in this energy level is Ws=as!ns!(asns)!


If one now considers all energy levels, the total number of possible states for the whole system is W=sWs

where s enumerates the energy levels. (I think countably infinitely many levels should not be a problem, would they?)


Now, one can try and maximize the entropy S=kln(W) under the constraints that the particle number is fixed, N=sns, as is the total energy, E=snsεs. Introducing the Lagrangian multipliers α and β in Λ:=Skα(snsN)β(snsεsE)

one indeed finds an extremum for Λ for ni=ai1+exp(α+βεi)
which is, up to a factor, the Fermi-Dirac statistic once the Lagrangian multipliers are identified to be α=μkBT and β=1kBT.


Now, in a side remark, the lecture notes claim that, if one had assumed a classical system where W=anss, one would have obtained Boltzmann statistics: ns=exp(αβϵs).


I assume that instead of W, the author meant to write Ws. From the form of Ws, I conclude that the system under consideration has discrete energy levels, and that the particles do not obey the Pauli principle and are distinguishable from one another. In these circumstances, anss seems to give the right number of configurations within the energy level ϵs, the total number of configurations again being W=sWs.



However, S now is linear in the ns, so that differentiation of the new Λ with regard to some ni gives an expression independent of any of the nk.


What went wrong? Why did the procedure seem to work in the first case, but not in this? Or did I make a (conceptual?) mistake somewhere along the line?


Any input would be greatly appreciated!



Answer



You are missing the term 1ns! from the product, i.e. W=sansns!

from which the wanted result follows.


Obviously in a quantum sense classical particles are distinguishable, so the term does not immediately arise from indistinguishability per se. Rather, the reason the "extra" term appears is because we ought to be looking at the macroscopic realizations of the system, and it does not matter for the macroscopic state if we switch two particles, and it is in this sense that they are indeed indistinguishable.


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