Phase behavior near and beyond the thermodynamic stability threshold

The phase behavior of stabilized dispersions of macromolecules is most easily described in terms of the effective interaction between the centers of mass of solute particles. For molecules such as polymer chains, dendrimers, etc., the effective pair potential is finite at the origin, allowing “particles” to freely interpenetrate each other. Using a double-Gaussian model (DGM) for demonstration, we study the behavior of the system as a function of the attraction strength $eta$. Above a critical strength $eta_c$, the infinite-size system is Ruelle unstable, in that it collapses to a cluster of finite volume. As $eta_c$ is approached from below, the liquid-vapor region exhibits an anomalous widening at low temperature, and the liquid density apparently diverges at the stability threshold. Above $eta_c$, the thermodynamic plane is divided in two regions, differing in the value of the average waiting time for collapse, being finite and small on one side of the boundary line, while large or even infinite in the other region. Upon adding a small hard core to the DGM potential, stability is fully recovered and the boundary line is converted to the spinodal line of a transition between fluid phases. We argue that the destabilization of a colloidal dispersion, as induced by the addition of salt or other flocculant, finds a suggestive analogy in the process by which a strengthening of the attraction pushes a stabilized-DGM system inside the fluid-fluid spinodal region.