Seeding approach to nucleation in the 
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 ensemble: The case of bubble cavitation in overstretched Lennard Jones fluids

Rosales-Pelaez, P.; Sanchez-Burgos, Ignacio; Valeriani, Chantal; Vega, Carlos; Sanz, Eduardo

doi:10.1103/physreve.101.022611

Cited by 36 publications

(58 citation statements)

References 55 publications

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“…It has been shown in different simulation works that spherical nuclei can be equilibrated at constant volume and temperature in finite systems [35,[44][45][46][47][48][49][50][51][52][53]. Recently, we showed with simulations of bubbles [54] and crystals [55] that nuclei thus equilibrated are critical, in agreement with Density Functional Theory (DFT) predictions [56,57]. On the other hand, we have extensively developed in the past years the so-called Seeding method [58][59][60][61] to study nucleation phenomena.…”

Section: Introductionsupporting

confidence: 52%

Equivalence between condensation and boiling in a Lennard Jones fluid

Sanchez-Burgos,

de Hijes,

Rosales-Pelaez

et al. 2021

Preprint

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Condensation and boiling are phase transitions highly relevant to industry, geology or atmospheric science. These phase transitions are initiated by the nucleation of a drop in a supersaturated vapor and of a bubble in an overstretched liquid respectively. The surface tension between both phases, liquid and vapor, is a key parameter in the development of such nucleation stage. Whereas the surface tension can be readily measured for a flat interface, there are technical and conceptual limitations to obtain it for the curved interface of the nucleus. On the technical side, it is quite difficult to observe a critical nucleus in experiments. From a conceptual point of view, the interfacial free energy depends on the choice of the dividing surface, being the surface of tension the one relevant for nucleation. We bypass the technical limitation by performing simulations of a Lennard Jones fluid where we equilibrate critical nuclei (both drops and bubbles). Regarding the conceptual hurdle, we find the relevant cluster size by searching the radius that correctly predicts nucleation rates and nucleation free energy barriers when combined with Classical Nucleation Theory. With such definition of the cluster size we find the same value of the surface tension for drops and bubbles of a given radius. Thus, condensation and boiling can be viewed as two sides of the same coin. Finally, we combine the data coming from drops and bubbles to obtain, via two different routes, estimates of the Tolman length, a parameter that allows describing the curvature dependence of the surface tension in a theoretical framework.

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Section: Introductionsupporting

confidence: 52%

Equivalence between condensation and boiling in a Lennard Jones fluid

Sanchez-Burgos,

de Hijes,

Rosales-Pelaez

et al. 2021

Preprint

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“…Hence, the clusters are critical at pressure p * . The fact that the nucleus equilibrated in the NVT ensemble is a critical cluster in the NpT ensemble has been recently shown for bubble cavitation in the Lennard Jones system 30 . In Fig.…”

Section: Resultsmentioning

confidence: 87%

“…The thermodynamics of systems having two phases with a curved interface is a fascinating topic that has been largely discussed by the scientific communities in the last decades [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] . A system with a fixed number of particles (N ), volume (V ), and temperature (T ) can exhibit a stable/metastable spherical interface between the solid and liquid phase corresponding to a global/local minimum of the Helmholtz free energy (F ) 2,5,15,[19][20][21][22][23][24][25][26][27][28][29][30] . Thermodynamic properties of metastable states can be studied as long as there is a free energy barrier separating them from the equilibrium one, and the relaxation time of the system is shorter than the time required to overcome the free energy barrier [31][32][33] .…”

Section: Introductionmentioning

confidence: 99%

Interfacial Free Energy and Tolman Length of Curved Liquid–Solid Interfaces from Equilibrium Studies

et al. 2020

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In this work, we study by means of simulations of hard spheres the equilibrium between a spherical solid cluster and the fluid. In the NVT ensemble we observe stable/metastable clusters of the solid phase in equilibrium with the fluid, representing configurations that are global/local minima of the Helmholtz free energy. Then, we run NpT simulations of the equilibrated system at the average pressure of the NVT run and observe that the clusters are critical because they grow/shrink with a probability of 1/2. Therefore, a crystal cluster equilibrated in the NVT ensemble corresponds to a Gibbs free energy maximum where the nucleus is in unstable equilibrium with the surrounding fluid, in accordance with what has been recently shown for vapor bubbles in equilibrium with the liquid. Then, within the Seeding framework, we use Classical Nucleation Theory to obtain both the interfacial free energy γ and the nucleation rate. The latter is in very good agreement with independent estimates using techniques that do not rely on Classical Nucleation Theory when the mislabeling criterion is used to identify the molecules of the solid cluster. We therefore argue that the radius obtained from the mislabeling criterion provides a good approximation for the radius of tension, R s . We obtain an estimate of the Tolman length by extrapolating the difference between R e (the Gibbs dividing surface) and R s to infinite radius. We show that such definition of the Tolman length coincides with that obtained by fitting γ versus 1/R s to a straight line as recently applied to hard spheres.

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“…We perform all simulations in a periodic cubic box of dimension length L = 27.5σ and vary the number of particles from 18,000 to 24,000 to explore a range of densities. This system size is such that the largest critical nucleus observed in this work was comprised of less than 4% of the particles in the system, to avoid the finite size effects that have been studied for seeded nucleation in the NVT ensemble [56]. For the determination of structure in longtime steady states, we run for 7200τ R and average over 10 independent configurations.…”

Section: Computer Simulationsmentioning

confidence: 99%

Crystallisation and polymorph selection in active Brownian particles

et al. 2021

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We explore crystallisation and polymorph selection in active Brownian particles with numerical simulation. In agreement with previous work (Wysocki et al. in Europhys Lett 105:48004, 2014), we find that crystallisation is suppressed by activity and occurs at higher densities with increasing Péclet number ($${ Pe }$$ Pe ). While the nucleation rate decreases with increasing activity, the crystal growth rate increases due to the accelerated dynamics in the melt. As a result of this competition, we observe the transition from a nucleation and growth regime at high $${ Pe }$$ Pe to “spinodal nucleation” at low $${ Pe }$$ Pe . Unlike the case of passive hard spheres, where preference for FCC over HCP polymorphs is weak, activity causes the annealing of HCP stacking faults, thus strongly favouring the FCC symmetry at high $${ Pe }$$ Pe . When freezing occurs more slowly, in the nucleation and growth regime, this tendency is much reduced and we see a trend towards the passive case of little preference for either polymorph.

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Seeding approach to nucleation in the NVT ensemble: The case of bubble cavitation in overstretched Lennard Jones fluids

Cited by 36 publications

References 55 publications

Equivalence between condensation and boiling in a Lennard Jones fluid

Equivalence between condensation and boiling in a Lennard Jones fluid

Interfacial Free Energy and Tolman Length of Curved Liquid–Solid Interfaces from Equilibrium Studies

Crystallisation and polymorph selection in active Brownian particles

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