bcc Symmetry in the Crystal-Melt Interface of Lennard-Jones Fluids Examined through Density Functional Theory

Shen, Yun‐Hwei; Oxtoby, David W.

doi:10.1103/physrevlett.77.3585

Cited by 111 publications

(91 citation statements)

References 21 publications

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“…In molecular dynamics (MD) of Lennard-Jones systems quenched not too close to the spinodal, evidence was found for nucleating droplets with an fcc core and a high degree of bcc ordering at the interface [30]. Consistent results were found in DFT studies of Lennard-Jones [31]. Subsequently, droplets of various other structures have been observed [32][33][34], indicating that nucleation phenomena in these models of atomistic crystallization is not fully controlled by proximity to a spinodal.…”

Section: Introductionsupporting

confidence: 66%

Liquid to solid nucleation via onion structure droplets

Barros

Klein

2013

The Journal of Chemical Physics

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We study homogeneous nucleation from a deeply quenched metastable liquid to a spatially modulated phase. We find, for a general class of density functional theories, that the universally favored nucleating droplet in dimensions d ≥ 3 is spherically symmetric with radial modulations resembling the layers of an onion. The existence of this droplet has important implications for systems with effective long-range interactions, and potentially applies to polymers, plasmas, and metals.

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Section: Introductionsupporting

confidence: 66%

Liquid to solid nucleation via onion structure droplets

Barros

Klein

2013

The Journal of Chemical Physics

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“…[15] This phenomenon is consistent with the results of a density functional calculation of liquid solid nucleation by Shen and Oxtoby. [21] Many systems of technological importance have long range, or effective long range interactions. These include polymers [11], neutral plasmas and metals.…”

Section: Summary and Discussionmentioning

confidence: 99%

Instability of Alexander-McTague crystals and its implication for nucleation

Klein

2001

Phys. Rev. E

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We show that the argument of Alexander and McTague, that the bcc crystalline structure is favored in those crystallization processes where the first order character is not too pronounced, is not correct. We find that any solution that satisfies the Alexander-McTague condition is not stable. We investigate the implication of this result for nucleation near the pseudo-spinodal in near-meanfield systems. † Permanent address

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“…This observation dates back to Ostwald, who formulated his famous ''step'' rule stating that the crystal phase that nucleates from the melt need not be the one that is thermodynamically most stable, but the one that is closest in free energy to the parent phase [1]. Recent simulations [2,3] and density-functional theory [4,5] provide an illustration on a microscopic scale that the vicinity of metastable phases may determine the properties of microscopic crystal nuclei. The relevant metastable phases need not be crystalline.…”

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confidence: 99%

Breakdown of Classical Nucleation Theory near Isostructural Phase Transitions

2004

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We report simulations of crystal nucleation in binary mixtures of hard spherical colloids with a size ratio of 1:10. The stable crystal phase of this system can be either dense or expanded. We find that, in the vicinity of the solid-solid critical point where the crystallites are highly compressible, small crystal nuclei are less dense than large nuclei. This phenomenon cannot be accounted for by either classical nucleation theory or by the Gibbsian droplet model. We argue that the observed behavior is due to the surface stress of the crystal nuclei. The observed effect highlights a general deficiency of the most frequently used thermodynamic theories for crystal nucleation. Surface stress should lead to an experimentally observable expansion of crystal nuclei of colloids with short-ranged attraction and of globular proteins. The pathway for crystal nucleation can be strongly influenced by the presence of metastable phases. This observation dates back to Ostwald, who formulated his famous ''step'' rule stating that the crystal phase that nucleates from the melt need not be the one that is thermodynamically most stable, but the one that is closest in free energy to the parent phase [1]. Recent simulations [2,3] and density-functional theory [4,5] provide an illustration on a microscopic scale that the vicinity of metastable phases may determine the properties of microscopic crystal nuclei. The relevant metastable phases need not be crystalline. For example, the presence of a critical demixing transition in the metastable liquid parent phase may have a dramatic effect on the nucleation process [3]. This scenario may be relevant for crystal nucleation in solutions of proteins or colloids, or in liquid metal alloys.Virtually nothing is known about the nucleation pathway for cases where the crystal phase that nucleates is close to a solid-solid critical point. Such situations can arise in the nucleation close to the critical point of an isostructural solid-solid transition. Isostructural solidsolid transitions are expected to occur in crystalline alloys near a substitutional order-disorder transition or in systems of hard colloidal particles with a short-ranged attraction [6 -9]. Here we consider the latter case. Depending on the range of attraction, the solid-solid critical point may either be located in a stable or in a metastable part of the phase diagram. Simulations by Dijkstra indicate that this is the case for mixtures of large and small hard colloids [9]. The small colloids (diameter s ) induce an effective attraction between the large colloids (diameter l ). The range of the attraction is determined by the size of the small colloids. For a size ratio q s = l 0:05, the phase diagram exhibits a stable isostructural critical point. For q 0:1 the range of attraction is longer and the isostructural critical point moves to the metastable region beyond the melting curve (see Fig. 1).We performed Monte Carlo simulations to investigate how the presence of a metastable critical point in the crystal phase affects the e...

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bcc Symmetry in the Crystal-Melt Interface of Lennard-Jones Fluids Examined through Density Functional Theory

Cited by 111 publications

References 21 publications

Liquid to solid nucleation via onion structure droplets

Liquid to solid nucleation via onion structure droplets

Instability of Alexander-McTague crystals and its implication for nucleation

Breakdown of Classical Nucleation Theory near Isostructural Phase Transitions

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