Past exam of the mathematics course of the University of Cambridge / 2023 / ii / Paper 2 / 37A / b

The mean extension in an ensemble of $A$ molecules iswith constraints ${\sum }_i{a}_i=A$ and ${\sum }_i{a}_i{l}_i=AL$. For occupancies $\{a_i\}$, the number of assignments of the $A$ distinguishable ensemble members to the states is the multinomial coefficientThus maximizing the probability at fixed $A$ and $L$ is equivalent to maximizing the stated Lagrange multiplier expression.

Because $A\gg 1$, the Stirling formula gives $\log (a_i!)\simeq a_i\log a_i-a_i$. Differentiating with respect to each $a_i$ givesNormalization by ${\sum }_i{a}_i=A$ therefore yields the probability mass functionHere $Z$ is the fixed-tension partition function that normalizes the probabilities.