Nonclassical Nucleation Pathways in Stacking-Disordered Crystals

The nucleation of crystals from liquid melt is often characterized by a competition between different crystalline structures or polymorphs and can result in nuclei with heterogeneous compositions. These mixed-phase nuclei can display nontrivial spatial arrangements, such as layered and onionlike str...

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Autores principales:	Fabio Leoni, John Russo
Formato:	article
Lenguaje:	EN
Publicado:	American Physical Society 2021
Materias:	Physics QC1-999
Acceso en línea:	https://doaj.org/article/d4aa1f78696a4ace831c98c0032a547a
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spelling	oai:doaj.org-article:d4aa1f78696a4ace831c98c0032a547a2021-12-02T15:21:58ZNonclassical Nucleation Pathways in Stacking-Disordered Crystals10.1103/PhysRevX.11.0310062160-3308https://doaj.org/article/d4aa1f78696a4ace831c98c0032a547a2021-07-01T00:00:00Zhttp://doi.org/10.1103/PhysRevX.11.031006http://doi.org/10.1103/PhysRevX.11.031006https://doaj.org/toc/2160-3308The nucleation of crystals from liquid melt is often characterized by a competition between different crystalline structures or polymorphs and can result in nuclei with heterogeneous compositions. These mixed-phase nuclei can display nontrivial spatial arrangements, such as layered and onionlike structures, whose composition varies according to the radial distance, and which so far have been explained on the basis of bulk and surface free-energy differences between the competing phases. Here we extend the generality of these nonclassical nucleation processes, showing that layered and onionlike structures can emerge solely based on structural fluctuations even in the absence of free-energy differences. We consider two examples of competing crystalline structures, hcp and fcc forming in hard spheres relevant for repulsive colloids and dense liquids, and the cubic and hexagonal diamond forming in water relevant also for other group 14 elements such as carbon and silicon. We introduce a novel structural order parameter that combined with a neural-network classification scheme allows us to study the properties of the growing nucleus from the early stages of nucleation. We find that small nuclei have distinct size fluctuations and compositions from the nuclei that emerge from the growth stage. The transition between these two regimes is characterized by the formation of onionlike structures, in which the composition changes with the distance from the center of the nucleus, similar to what is seen in the two-step nucleation process.Fabio LeoniJohn RussoAmerican Physical SocietyarticlePhysicsQC1-999ENPhysical Review X, Vol 11, Iss 3, p 031006 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Physics QC1-999
spellingShingle	Physics QC1-999 Fabio Leoni John Russo Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
description	The nucleation of crystals from liquid melt is often characterized by a competition between different crystalline structures or polymorphs and can result in nuclei with heterogeneous compositions. These mixed-phase nuclei can display nontrivial spatial arrangements, such as layered and onionlike structures, whose composition varies according to the radial distance, and which so far have been explained on the basis of bulk and surface free-energy differences between the competing phases. Here we extend the generality of these nonclassical nucleation processes, showing that layered and onionlike structures can emerge solely based on structural fluctuations even in the absence of free-energy differences. We consider two examples of competing crystalline structures, hcp and fcc forming in hard spheres relevant for repulsive colloids and dense liquids, and the cubic and hexagonal diamond forming in water relevant also for other group 14 elements such as carbon and silicon. We introduce a novel structural order parameter that combined with a neural-network classification scheme allows us to study the properties of the growing nucleus from the early stages of nucleation. We find that small nuclei have distinct size fluctuations and compositions from the nuclei that emerge from the growth stage. The transition between these two regimes is characterized by the formation of onionlike structures, in which the composition changes with the distance from the center of the nucleus, similar to what is seen in the two-step nucleation process.
format	article
author	Fabio Leoni John Russo
author_facet	Fabio Leoni John Russo
author_sort	Fabio Leoni
title	Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
title_short	Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
title_full	Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
title_fullStr	Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
title_full_unstemmed	Nonclassical Nucleation Pathways in Stacking-Disordered Crystals
title_sort	nonclassical nucleation pathways in stacking-disordered crystals
publisher	American Physical Society
publishDate	2021
url	https://doaj.org/article/d4aa1f78696a4ace831c98c0032a547a
work_keys_str_mv	AT fabioleoni nonclassicalnucleationpathwaysinstackingdisorderedcrystals AT johnrusso nonclassicalnucleationpathwaysinstackingdisorderedcrystals
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Nonclassical Nucleation Pathways in Stacking-Disordered Crystals

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