Phase transitions are uncommon among homogeneous one-dimensional fluids of classical particles owing to a general nonexistence result due to van Hove. A way to circumvent van Hove’s theorem is to consider an interparticle potential that is finite everywhere. Of this type is the generalized exponential model of index 4 (GEM4 potential), a model interaction which in three dimensions provides an accurate description of the effective pair repulsion between dissolved soft macromolecules (e.g., flexible dendrimers). Using specialized free-energy methods, I reconstruct the equilibrium phase diagram of the one-dimensional GEM4 system, showing that, apart from the usual fluid phase at low densities, it consists of an endless sequence of cluster fluid phases of increasing pressure, having a sharp crystal appearance for low temperatures. The coexistence line between successive phases in the sequence invariably terminates at a critical point. Focussing on the first of such transitions, I show that the growth of the two-cluster phase from the metastable ordinary fluid is extremely slow, even for large supersaturations. Finally, I clarify the apparent paradox of the observation of an activation barrier to nucleation in a system where, due to the dimensionality of the hosting space, the critical radius is expected to vanish.
Cluster phases of penetrable rods on a line
PRESTIPINO GIARRITTA, Santi
2014-01-01
Abstract
Phase transitions are uncommon among homogeneous one-dimensional fluids of classical particles owing to a general nonexistence result due to van Hove. A way to circumvent van Hove’s theorem is to consider an interparticle potential that is finite everywhere. Of this type is the generalized exponential model of index 4 (GEM4 potential), a model interaction which in three dimensions provides an accurate description of the effective pair repulsion between dissolved soft macromolecules (e.g., flexible dendrimers). Using specialized free-energy methods, I reconstruct the equilibrium phase diagram of the one-dimensional GEM4 system, showing that, apart from the usual fluid phase at low densities, it consists of an endless sequence of cluster fluid phases of increasing pressure, having a sharp crystal appearance for low temperatures. The coexistence line between successive phases in the sequence invariably terminates at a critical point. Focussing on the first of such transitions, I show that the growth of the two-cluster phase from the metastable ordinary fluid is extremely slow, even for large supersaturations. Finally, I clarify the apparent paradox of the observation of an activation barrier to nucleation in a system where, due to the dimensionality of the hosting space, the critical radius is expected to vanish.Pubblicazioni consigliate
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