Physics Asked by Syrocco on March 30, 2021
I’m having some trouble understanding the formula: $Z=e^{-beta F}$ which is sometimes used to define the partition function.
From what I understand, this $Z$, is the partition function but taken at the thermodynamic limit since:
$$Z=sum_{E_i}Omega(E_i)e^{-beta E_i}=sum_{E_i}e^{S_m(E_i)/k_b}e^{-beta E_i}=sum_{E_i}e^{beta(S_m(E_i)T- E_i)}=sum_{E_i}e^{-beta F(E_i)}$$
And then, by taking the thermodynamic limit; we would find that $F$ is minimal at $E^*$ (which is approximatively equal to $bar{E}$) and because $F$ is (inversely) peaked at $E^*$ we could write:
$$Z=sum_{E_i}e^{-beta F(E_i)}simeq e^{-beta F(bar{E})}$$
And then, saying that $Z=e^{-beta F}$ would be an approximation a bit like writing: $Z=Omega(bar{E})e^{-betabar{E}}$.
Is this right? Or am I missing something?
note:
I’am not even sure I can write $E_i-TS_m(E_i)=F(E_i)$ since $S_m$ is the microcanonical entropy and not the thermodynamic one nor the canonical one (I guess?)…
Is it right too, to write $F$ as a function of the energy, in this case? Since it is supposed to be a function of $V$ and $T$?
We could also define $F$ from: $F=bar{E}-TS$ and then, from $S=k_bfrac{partial Tln(Z)}{partial T}$ and $bar{E}=- frac{partial ln Z}{partial beta}$ but we are still using a thermodynamic relation and not an "exact" one?
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