Physics – Condensed Matter – Soft Condensed Matter
Scientific paper
2011-07-15
J. Chem. Phys. 136, 061102 (2012)
Physics
Condensed Matter
Soft Condensed Matter
Scientific paper
10.1063/1.3685804
We show that for any liquid or solid with strong correlation between its $NVT$ virial and potential-energy equilibrium fluctuations, the temperature is a product of a function of excess entropy per particle and a function of density, $T=f(s)h(\rho)$. This implies that 1) the system's isomorphs (curves in the phase diagram of invariant structure and dynamics) are described by $h(\rho)/T={\rm Const.}$, 2) the density-scaling exponent is a function of density only, 3) a Gr{\"u}neisen-type equation of state applies for the configurational degrees of freedom. For strongly correlating atomic systems one has $h(\rho)=\sum_nC_n\rho^{n/3}$ in which the only non-zero terms are those appearing in the pair potential expanded as $v(r)=\sum_n v_n r^{-n}$. Molecular dynamics simulations of Lennard-Jones type systems confirm the theory.
Bøhling Lasse
Dyre Jeppe C.
Ingebrigtsen Trond S.
Schrøder Thomas B.
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