Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs
Abstract
Complex crystallization pathways are common in protein crystallization, tetrahedrally coordinated systems, and biomineralization, where single or multiple precursors temporarily appear before the formation of the crystal. The emergence of precursors is often explained by a unique property of the system, such as short-range attraction, directional bonding, or ion association. But, structural characteristics of the prenucleation phases found in multistep crystallization remain unclear, and models are needed for testing and expanding the understanding of fluid-to-solid ordering pathways. Here, we report 3 instances of 2-step crystallization of hard-particle fluids. Crystallization in these systems proceeds via a high-density precursor fluid phase with prenucleation motifs in the form of clusters, fibers and layers, and networks, respectively. The density and diffusivity change across the fluid–fluid phase transition increases with motif dimension. We observe crystal nucleation to be catalyzed by the interface between the 2 fluid phases. The crystals that form are complex, including, notably, a crystal with 432 particles in the cubic unit cell. Finally, our results establish the existence of complex crystallization pathways in entropic systems and reveal prenucleation motifs of various dimensions.
- Authors:
-
- Univ. of Michigan, Ann Arbor, MI (United States)
- Univ. of Michigan, Ann Arbor, MI (United States); Friedrich-Alexander Univ. Erlangen-Nurnberg (Germany)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); DGE 1256260; ACI-1053575
- OSTI Identifier:
- 1610454
- Grant/Contract Number:
- SC0000989; DMR 1409620
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 116; Journal Issue: 30; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 59 BASIC BIOLOGICAL SCIENCES; colloidal crystallization; 2-step crystallization; fluid-fluid phase transitions; liquid-liquid phase; transition; entropic crystallization
Citation Formats
Lee, Sangmin, Teich, Erin G., Engel, Michael, and Glotzer, Sharon C. Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs. United States: N. p., 2019.
Web. doi:10.1073/pnas.1905929116.
Lee, Sangmin, Teich, Erin G., Engel, Michael, & Glotzer, Sharon C. Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs. United States. https://doi.org/10.1073/pnas.1905929116
Lee, Sangmin, Teich, Erin G., Engel, Michael, and Glotzer, Sharon C. Mon .
"Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs". United States. https://doi.org/10.1073/pnas.1905929116. https://www.osti.gov/servlets/purl/1610454.
@article{osti_1610454,
title = {Entropic colloidal crystallization pathways via fluid–fluid transitions and multidimensional prenucleation motifs},
author = {Lee, Sangmin and Teich, Erin G. and Engel, Michael and Glotzer, Sharon C.},
abstractNote = {Complex crystallization pathways are common in protein crystallization, tetrahedrally coordinated systems, and biomineralization, where single or multiple precursors temporarily appear before the formation of the crystal. The emergence of precursors is often explained by a unique property of the system, such as short-range attraction, directional bonding, or ion association. But, structural characteristics of the prenucleation phases found in multistep crystallization remain unclear, and models are needed for testing and expanding the understanding of fluid-to-solid ordering pathways. Here, we report 3 instances of 2-step crystallization of hard-particle fluids. Crystallization in these systems proceeds via a high-density precursor fluid phase with prenucleation motifs in the form of clusters, fibers and layers, and networks, respectively. The density and diffusivity change across the fluid–fluid phase transition increases with motif dimension. We observe crystal nucleation to be catalyzed by the interface between the 2 fluid phases. The crystals that form are complex, including, notably, a crystal with 432 particles in the cubic unit cell. Finally, our results establish the existence of complex crystallization pathways in entropic systems and reveal prenucleation motifs of various dimensions.},
doi = {10.1073/pnas.1905929116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 30,
volume = 116,
place = {United States},
year = {Mon Jul 08 00:00:00 EDT 2019},
month = {Mon Jul 08 00:00:00 EDT 2019}
}
Web of Science
Figures / Tables:
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Works referencing / citing this record:
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Figures / Tables found in this record: