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Upon osmotic compression, rotationally symmetric faceted colloidal particles can form translationally ordered, orientationally disordered rotator mesophases. This study explores the mechanism of rotator-to-crystal phase transitions where orientational order is gained in a translationally ordered phase, using rotator-phase forming truncated cubes as a testbed. Monte Carlo simulations were conducted for two selected truncations (s), one for s = 0.527 where the rotator and crystal lattices are dissimilar and one for s = 0.572 where the two phases have identical lattices. These differences set the stage for a qualitative difference in their rotator–crystal transitions, highlighting the effect of lattice distortion on phase transition kinetics. Our simulations reveal that significant lattice deviatoric effects could hinder the rotator-to-crystal transition and favor arrangements of lower packing fraction instead. Indeed, upon compression, it is found that for s = 0.527, the rotator phase does not spontaneously transition into the stable, densely packed crystal due to the high lattice strains involved but instead transitions into a metastable solid phase to be colloquially referred to as “orientational salt” for short, which has a similar lattice as the rotator phase and exhibits two distinct particle orientations having substitutional order, alternating regularly throughout the system. This study paves the way for further analysis of diffusionless transformations in nanoparticle systems and how lattice-distortion could influence crystallization kinetics.
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Symmetries in hard polygon systems determine plastic colloidal crystal mesophases in two dimensions
Orientational ordering is a necessary step in the crystallization of molecules and anisotropic colloids. Plastic crystals, which are possible mesophases between the fluid and fully ordered crystal, are translationally ordered but exhibit no long range orientational order. Here, we study the two-dimensional phase behavior of hard regular polygons with edge number n = 3–12. This family of particles provides a model system to isolate the effect of shape and symmetry on the existence of plastic crystal phases. We show that the symmetry group of the particle, G , and the symmetry group of the local environment in the crystal, H , together determine plastic colloidal crystal phase behavior in two dimensions. If G contains completely the symmetry elements of H , then a plastic crystal phase is absent. If G and H share some but not all nontrivial symmetry elements, then a plastic crystal phase exists with preferred particle orientations that recover the absent symmetry elements of the crystal; we call this phase the discrete plastic crystal phase. If G and H share no nontrivial symmetry elements, then a plastic crystal phase exists without preferred orientations, which we call an indiscrete plastic crystal.
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- Award ID(s):
- 1409620
- PAR ID:
- 10090824
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 15
- Issue:
- 12
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 2571 to 2579
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9SM00016J
