Statistical Mechanics, Simplifying dq/dT

AI Thread Summary
The discussion centers on the derivation of the average energy in statistical mechanics, specifically how to simplify the expression for dq/dT. The participant is trying to understand why the sum of g_i ε_i is considered the mean energy without dividing by the number of states, questioning if it represents total molecular energy instead. They clarify that the probability of a particle having energy ε_i is given by a specific formula, which leads to the calculation of average energy using this probability. The conversation emphasizes the importance of correctly interpreting the average molecular energy and its relation to the partition function. Understanding these concepts is crucial for accurately applying statistical mechanics principles.
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Homework Statement



\frac{dq}{dT}=\sum_{i} g_i \frac{dq}{dT} e^{-\frac{ε_i}{kT}} = \frac{1}{kT^2}\sum_{i} g_i ε_i e^{-\frac{ε_i}{kT}} = \frac{1}{kT^2} \bar{ε} q

Homework Equations



q=\sum_{i} e^{-\frac{ε_i}{kT}} or for degenerate states, q=\sum_{I} g_i e^{-\frac{ε_I}{kT}}

The Attempt at a Solution



The equations in (1) are just set out in my notes. My problem is understanding the last step: I take \bar{ε} to be the average molecular energy, since later they show that \bar{ε}_{trans}=\frac{3}{2}kT.

How can \sum_{i} g_i ε_i be the mean, without dividing by N? Isn't it the total molecular energy?
 
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The probability for a particle to have energy ##\varepsilon_i## is
$$
\mathcal{P}(\varepsilon_i) = \frac{1}{q} g_i e^{-\varepsilon_i / kT}
$$
Therefore, the average energy can be calculated as
$$
\begin{align}
\bar{\varepsilon} &= \sum_i \varepsilon_i \mathcal{P}(\varepsilon_i) \\
&= \sum_i \varepsilon_i \frac{1}{q} g_i e^{-\varepsilon_i / kT}
\end{align}
$$
Compare to your equation.
 
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