Physics Asked on May 8, 2021
The Helmholtz free energy is defined by the difference between the internal energy and the entropy of the system,
$$F_{T} = U_{T} + kTH_{T},$$
where $U_{T} = sum_s P_{T}(s)E(s)$ is the internal energy of a state $s$ and $H_{T} = -sum_s P_{T}(s) log P_{T}(s)$ is the entropy. Why $P_{T}(s)$ is the Boltzmann distribution when $F$ is minimized?
I try to minimize $F_{T}$ w.r.t. $P_{T}(s)$ but fail to obtain the Boltzmann distribution.
$$begin{aligned}
& frac{d F_{T}}{d P_{T}(s)}= E_{s}-k T left[log P_{T}(s) + 1right] = 0
& Rightarrow E_{s} = k T left[log P_{T}(s) + 1right]
& Rightarrow P_{T}(s) = exp(frac{E_{s}}{k T}-1) quad s.t. quad sum_s P_{T}(s) = 1
& Rightarrow P_{T}(s) = exp left( frac{E_{s}}{k T}- sum_s exp(frac{E_{s}}{k T}-1) right)
& Rightarrow P_{T}(s) = frac{exp (frac{E_{s}}{k T})}{sum_s exp(frac{E_{s}}{k T}-1) }
end{aligned}$$
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