Long-range interacting systems and the Gibbs-Duhem equation

The generalized Gibbs-Duhem equation is obtained for systems with long-range interactions in $d$ spatial dimensions. We consider that particles in the system interact through a slowly decaying pair potential of the form $1/r^ν$ with $0\leqν\leq d$. The local equation of state is obtained by computing the local entropy per particle and using the condition of local thermodynamic equilibrium. This local equation of state turns out to be that of an ideal gas. Integrating the relation satisfied by local thermodynamic variables over the volume, the equation involving global magnitudes is derived. Thus, the Euler relation is found and we show that it is modified by the addition of a term proportional to the total potential energy. This term is responsible for the modification of the Gibbs-Duhem equation. We also point out a close relationship between the thermodynamics of long-range interacting systems and the thermodynamics of small systems introduced by Hill.

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