[Physics] Proof of the generalized equipartition theorem

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The generalized equipartition theorem (where variables need not be quadratic) states that if $x_i$ is a canonical variable (position or momentum variable), then

$$\left\langle x_i \frac{\partial \mathcal{H}}{\partial x_j}\right\rangle = \delta_{ij}\ k T$$

where the average $\langle \cdot \rangle$ is taken over an equilibrium probability density $\rho(p,q)$:

$$\langle f(p,q) \rangle = \int dp dq \ \rho(p,q) \ f(p,q)$$

In the most general case this probability density is the canonical ensemble's. For the theorem to hold ergodicity is also required. However, I'm having trouble finding a rigorous prove where the assumptions are explicitly used in the derivation.

Could you provide such a prove, or a reference to a paper/book where it can be found?

Best Answer

J. A. S. Lima and A. R. Plastino published the article On the classical energy equipartition theorem back in 1999. In their article they derive a generalized equipartition theorem. Their generalized approach is valid for systems with arbitrary distribution functions and for systems with non-quadratic terms in the Hamiltionian. A link to their article is https://doi.org/10.1590/S0103-97332000000100019. This article should answer most of your questions.

Their article can be summarized as follows:

Suppose there is a system with $f$ degrees of freedom and the Hamiltonian is \begin{equation} \mathcal{H} = g(x_1,...,x_L) + h. \end{equation} $(x_1,...,x_L)$ is a subset of the phase-space coordinates for positions and momentas. $g$ is homogeneous such that

\begin{equation} g\left(\lambda x_{1}, \ldots, \lambda x_{L}\right)=\lambda^{r} g\left(x_{1}, \ldots, x_{L}\right). \end{equation} For systems that are distributed according to a Boltzmann distribution you can derive the expression

\begin{equation} \langle g\rangle=\frac{L}{r} k_B T. \end{equation} Here $k_B$ is the Boltzmann constant and $T$ is the temperature. This is the generalized form of the equipartition theorem that you are looking for. For example, for a monovalent ideal gas you have $r=2$ and $L=3N$ such that you recover the famous result $U = \frac{3}{2}N k_B T$ where U is the internal energy of the gas.

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