Shape and area fluctuation effects on nucleation theory

In standard nucleation theory, the nucleation process is characterized by computing \u394\u3a9(V), the reversible work required to form a cluster of volume V of the stable phase inside the metastable mother phase. However, other quantities besides the volume could play a role in the free energy of cluster formation, and this will in turn affect the nucleation barrier and the shape of the nucleus. Here we exploit our recently introduced mesoscopic theory of nucleation to compute the free energy cost of a nearly spherical cluster of volume V and a fluctuating surface area A, whereby the maximum of \u394\u3a9(V) is replaced by a saddle point in \u394\u3a9(V, A). Compared to the simpler theory based on volume only, the barrier height of \u394\u3a9(V, A) at the transition state is systematically larger by a few kBT. More importantly, we show that, depending on the physical situation, the most probable shape of the nucleus may be highly non-spherical, even when the surface tension and stiffness of the model are isotropic. Interestingly, these shape fluctuations do not influence or modify the standard Classical Nucleation Theory manner of extracting the interface tension from the logarithm of the nucleation rate near coexistence

Systematic Improvement of Classical Nucleation Theory

We reconsider the applicability of classical nucleation theory (CNT) to the calculation of the free energy of solid cluster formation in a liquid and its use to the evaluation of interface free energies from nucleation barriers. Using two different freezing transitions (hard spheres and NaCl) as test cases, we first observe that the interface-free-energy estimates based on CNT are generally in error. As successive refinements of nucleation-barrier theory, we consider corrections due to a non-sharp solid-liquid interface and to a non-spherical cluster shape. Extensive calculations for the Ising model show that corrections due to a non-sharp and thermally fluctuating interface account for the barrier shape with excellent accuracy. The experimental solid nucleation rates that are measured in colloids are better accounted for by these non-CNT terms, whose effect appears to be crucial in the interpretation of data and in the extraction of the interface tension from them.Comment: 20 pages (text + supplementary material

A fingerprint of surface-tension anisotropy in the free-energy cost of nucleation

We focus on the Gibbs free energy \u394G for nucleating a droplet of the stable phase (e.g. solid) inside the metastable parent phase (e.g. liquid), close to the first-order transition temperature. This quantity is central to the theory of homogeneous nucleation, since it superintends the nucleation rate. We recently introduced a field theory describing the dependence of \u394G on the droplet volume V, taking into account besides the microscopic fuzziness of the droplet-parent interface, also small fluctuations around the spherical shape whose effect, assuming isotropy, was found to be a characteristic logarithmic term. Here we extend this theory, introducing the effect of anisotropy in the surface tension, and show that in the limit of strong anisotropy \u394G(V) once more develops a term logarithmic on V, now with a prefactor of opposite sign with respect to the isotropic case. Based on this result, we argue that the geometrical shape that large solid nuclei mostly prefer could be inferred from the prefactor of the logarithmic term in the droplet free energy, as determined from the optimization of its near-coexistence profile

A variational mean-field study of clusterization in a zero-temperature system of soft-core bosons

We work out the ground-state diagram of weakly-repulsive penetrable bosons, using mean-field theory with a Gaussian ansatz on the single-particle wave function. Upon compression, the fluid transforms into a cluster supersolid, whose structure is characterized for various choices of the embedding space. In Euclidean space, the stable crystals are those with the most compact structure, i.e., triangular and fcc in two and three dimensions, respectively. For particles confined in a spherical surface, as the sphere radius increases we observe a sequence of transitions between different cluster phases, all having a regular or semiregular polyhedron as supporting frame for the clusters. The present results are relevant for the behavior of ultracold bosons weakly coupled to a Rydberg state

A variational mean-field study of clusterization in a zero-temperature system of soft-core bosons

We work out the ground-state diagram of weakly-repulsive penetrable bosons, using mean-field theory with a Gaussian ansatz on the single-particle wave function. Upon compression, the fluid transforms into a cluster supersolid, whose structure is characterized for various choices of the embedding space. In Euclidean space, the stable crystals are those with the most compact structure, i.e., triangular and fcc in two and three dimensions, respectively. For particles confined in a spherical surface, as the sphere radius increases we observe a sequence of transitions between different cluster phases, all having a regular or semiregular polyhedron as supporting frame for the clusters. The present results are relevant for the behavior of ultracold bosons weakly coupled to a Rydberg state