pith. sign in

arxiv: 1208.3089 · v2 · pith:4RYCEMY7new · submitted 2012-08-15 · ❄️ cond-mat.soft · cond-mat.stat-mech· physics.chem-ph

Class of consistent fundamental-measure free energies for hard-sphere mixtures

classification ❄️ cond-mat.soft cond-mat.stat-mechphysics.chem-ph
keywords alphafundamental-measurebulkdensitiesdensityfreefree-energyhard-sphere
0
0 comments X
read the original abstract

In fundamental-measure theories the bulk excess free-energy density of a hard-sphere fluid mixture is assumed to depend on the partial number densities ${\rho_i}$ only through the four scaled-particle-theory variables ${\xi_\alpha}$, i.e., $\Phi({\rho_i})\to\Phi({\xi_\alpha})$. By imposing consistency conditions, it is proven here that such a dependence must necessarily have the form $\Phi({\xi_\alpha})=-\xi_0\ln(1-\xi_3)+\Psi(y)\xi_1\xi_2/(1-\xi_3)$, where $y\equiv {\xi_2^2}/{12\pi \xi_1 (1-\xi_3)}$ is a scaled variable and $\Psi(y)$ is an arbitrary dimensionless scaling function which can be determined from the free-energy density of the one-component system. Extension to the inhomogeneous case is achieved by standard replacements of the variables ${\xi_\alpha}$ by the fundamental-measure (scalar, vector, and tensor) weighted densities ${n_\alpha(\mathbf{r})}$. Comparison with computer simulations shows the superiority of this bulk free energy over the White Bear one.

This paper has not been read by Pith yet.

discussion (0)

Sign in with ORCID, Apple, or X to comment. Anyone can read and Pith papers without signing in.