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A common approach to study nucleation rates is the estimation of free-energybarriers. This usually requires knowledge about the shape of the formingdroplet, a task that becomes notoriously difficult in macromolecular setupsstarting with a proper definition of the cluster boundary. Here, we demonstratea shape-free determination of the free energy for temperature-driven clusterformation in particle as well as polymer systems. Combined with rigorousresults on equilibrium droplet formation, this allows for a well-definedfinite-size scaling analysis of the effective interfacial free energy at fixeddensity. We first verify the theoretical predictions for the formation of aliquid droplet in a supersaturated particle gas by generalized-ensemble MonteCarlo simulations of a Lennard-Jones system. Going one step further, we thengeneralize this approach to cluster formation in a dilute polymer solution. Ourresults suggest an analogy with particle condensation, when the macromoleculesare interpreted as extended particles.

Canonical free-energy barrier of particle and polymer cluster formation