Within this work, we derive and analyse an expression for the free energy of a single-species system in the thermodynamic limit in terms of a generalised cavity volume, that is exact in general, and in principle applicable to systems across their entire range of density, as well as to particles within a general coordinate space. This provides a universal equation of state, and can thus relate the cavity volume to classical results, such as Mayer’s cluster expansions. Through this, we are able to provide some insight into the connections between cavity volume and free energy density, as well as their consequences. We use examples which permit explicit computations to further probe these results, reclaiming the exact results for a classical Tonks gas and providing a novel derivation of Onsager’s free energy for a single species, isotropic system. Given the complexity of the problem, we also provide a local lattice ansatz, exact in one dimension, with which we may approximate the cavity volume for hard sphere systems to provide an accurate equation of state in the cases of hard disks and spheres in both dilute regimes as well as beyond the freezing transition.

Cavity Volume and Free Energy in Many-Body Systems

Virga E. G.;
2021

Abstract

Within this work, we derive and analyse an expression for the free energy of a single-species system in the thermodynamic limit in terms of a generalised cavity volume, that is exact in general, and in principle applicable to systems across their entire range of density, as well as to particles within a general coordinate space. This provides a universal equation of state, and can thus relate the cavity volume to classical results, such as Mayer’s cluster expansions. Through this, we are able to provide some insight into the connections between cavity volume and free energy density, as well as their consequences. We use examples which permit explicit computations to further probe these results, reclaiming the exact results for a classical Tonks gas and providing a novel derivation of Onsager’s free energy for a single species, isotropic system. Given the complexity of the problem, we also provide a local lattice ansatz, exact in one dimension, with which we may approximate the cavity volume for hard sphere systems to provide an accurate equation of state in the cases of hard disks and spheres in both dilute regimes as well as beyond the freezing transition.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11571/1441034
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