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Abstract
Introduction
Results
Conclusions
Extended Common Neighbor Analysis (Ext-Cna)
Q4 Q6 Sensitivity to Protocols
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Nonclassical Nucleation Pathways in Stacking-Disordered Crystals

Profile image of Fabio LeoniFabio Leoni

2021

https://doi.org/10.1103/PHYSREVX.11.031006
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Abstract

The nucleation of crystals from the 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 onion-like 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 non-classical nucleation processes, showing that layered and onion-like structures can emerge solely based on structural fluctuations even in 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 intro...

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Tanja Schilling

The Journal of chemical physics, 2016

We investigate the early part of the crystal nucleation process in the hard sphere fluid using data produced by computer simulation. We find that hexagonal order manifests continuously in the overcompressed liquid, beginning approximately one diffusion time before the appearance of the first &quot;solid-like&quot; particle of the nucleating cluster, and that a collective influx of particles towards the nucleation site occurs simultaneously to the ordering process: the density increases leading to nucleation are generated by the same individual particle displacements as the increases in order. We rule out the presence of qualitative differences in the early nucleation process between medium and low overcompressions and also provide evidence against any separation of translational and orientational order on the relevant lengthscales.

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Crystal Nucleation in the Hard-Sphere System Revisited: A Critical Test of Theoretical Approaches
László Gránásy

The Journal of Physical Chemistry B, 2009

The hard sphere system is the best known fluid that crystallizes: the solid-liquid interfacial free energy, the equations of state, and the height of the nucleation barrier are known accurately, offering a unique possibility for a quantitative validation of nucleation theories. A recent significant downward revision of the interfacial free energy from ~ 0.61 kT/σ 2 to (0.56 ± 0.02) kT/σ 2 [Davidchack, R.; Morris, J. R.; Laird, B. B. J. Chem. Phys. 2006, 125, 094710] necessitates a re-evaluation of theoretical approaches to crystal nucleation. This have been carried out for the droplet model of the classical nucleation theory (CNT), the self-consistent classical theory (SCCT), a phenomenological diffuse interface theory (DIT), and single and two-field variants of the phase field theory that rely on either the usual double well and interpolation functions (PFT/S1 an PFT/S2, respectively) or on a Ginzburg-Landau expanded free energy that reflects the crystal symmetries (PFT/GL1 and PFT/GL2). We find that the PFT/GL1, PFT/GL2 and the DIT models predict fairly accurately the height of the nucleation barrier known from Monte Carlo simulations in the volume fraction range of 0.52 < φ < 0.54, whereas the CNT, SCCT, PFT/S1 and PFT/S2 models underestimate it significantly.

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Kinetic Phase Diagram for Nucleation and Growth of Competing Crystal Polymorphs in Charged Colloids
Marjolein Dijkstra

Physical Review Letters, 2022

We determine the full kinetic phase diagram for nucleation and growth of crystal phases in a suspension of charged colloids. We calculate nucleation barrier heights for face-centered cubic (fcc) and body-centered cubic (bcc) crystal phases for varying screening lengths and supersaturations using the seeding approach in extensive simulations. Using classical nucleation theory, we determine for the entire metastable fluid region the crystal polymorph with the lowest nucleation barrier. Surprisingly, we find a regime close to the triple point where metastable bcc can form due to a lower nucleation barrier, even though fcc is the stable phase. For higher supersaturation, we find that the difference in barrier heights decreases and we observe a mix of hexagonal close-packed (hcp), fcc and bcc structures in the growth of crystalline seeds as well as in spontaneously formed crystals.

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Cited by

The physics of empty liquids: from patchy particles to water
Fabio Leoni

Reports on Progress in Physics, 2022

Empty liquids represent a wide class of materials whose constituents arrange in a random network through reversible bonds. Many key insights on the physical properties of empty liquids have originated almost independently from the study of colloidal patchy particles on one side, and a large body of theoretical and experimental research on water on the other side. Patchy particles represent a family of coarse-grained potentials that allows for a precise control of both the geometric and the energetic aspects of bonding, while water has arguably the most complex phase diagram of any pure substance, and a puzzling amorphous phase behavior. It was only recently that the exchange of ideas from both fields has made it possible to solve long-standing problems and shed new light on the behavior of empty liquids. Here we highlight the connections between patchy particles and water, focusing on the modelling principles that make an empty liquid behave like water, including the factors that co...

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Crystal Polymorph Selection Mechanism of Hard Spheres Hidden in the Fluid
Marjolein Dijkstra

ACS Nano, 2023

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Signatures of sluggish dynamics and local structural ordering during ice nucleation
Fausto Martelli

The Journal of Chemical Physics, 2022

We investigate the microscopic pathway of spontaneous crystallization in the ST2 model of water under deeply supercooled conditions via unbiased classical molecular dynamics simulations. After quenching below the liquid–liquid critical point, the ST2 model spontaneously separates into low-density liquid (LDL) and high-density liquid phases, respectively. The LDL phase, which is characterized by lower molecular mobility and enhanced structural order, fosters the formation of a sub-critical ice nucleus that, after a stabilization time, develops into the critical nucleus and grows. Polymorphic selection coincides with the development of the sub-critical nucleus and favors the formation of cubic (Ic) over hexagonal (Ih) ice. We rationalize polymorphic selection in terms of geometric arguments based on differences in the symmetry of second neighbor shells of ice Ic and Ih, which are posited to favor formation of the former. The rapidly growing critical nucleus absorbs both Ic and Ih crys...

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