Size-dependent thermodynamic structural selection in colloidal crystallization

Pretti, Evan; Zerze, Hasan; Song, Minseok; Ding, Yajun; Mao, Runfang; Mittal, Jeetain

doi:10.1126/sciadv.aaw5912

Cited by 11 publications

(16 citation statements)

References 30 publications

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“…Any potential entropic factors, such as differing configurational entropies across the different pathways, would be present in all of the simulation types and therefore could not be responsible for the differences we observe with and without hydrodynamics. Nonetheless, we note that thermodynamic selection has been shown to be relevant in similar but reversible systems governed by the differences in the surface energies of small crystallites (40). Indeed, this system would likely require further engineering to achieve reversible switching/adaptive capability, possibly using sequential addition of additional DNA oligomers to alter the binding energetics as in ref.…”

Section: Discussionmentioning

confidence: 92%

Hydrodynamic and frictional modulation of deformations in switchable colloidal crystallites

Lee¹,

Li²,

Perdikaris³

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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Displacive transformations in colloidal crystals may offer a pathway for increasing the diversity of accessible configurations without the need to engineer particle shape or interaction complexity. To date, binary crystals composed of spherically symmetric particles at specific size ratios have been formed that exhibit floppiness and facile routes for transformation into more rigid structures that are otherwise not accessible by direct nucleation and growth. There is evidence that such transformations, at least at the micrometer scale, are kinetically influenced by concomitant solvent motion that effectively induces hydrodynamic correlations between particles. Here, we study quantitatively the impact of such interactions on the transformation of binary bcc-CsCl analog crystals into close-packed configurations. We first employ principal-component analysis to stratify the explorations of a bcc-CsCl crystallite into orthogonal directions according to displacement. We then compute diffusion coefficients along the different directions using several dynamical models and find that hydrodynamic correlations, depending on their range, can either enhance or dampen collective particle motions. These two distinct effects work synergistically to bias crystallite deformations toward a subset of the available outcomes.

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Section: Discussionmentioning

confidence: 92%

Hydrodynamic and frictional modulation of deformations in switchable colloidal crystallites

Lee¹,

Li²,

Perdikaris³

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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“…Previous work with the aforementioned two-dimensional system has shown that under such conditions, nucleation barriers are negligible or the critical nuclei sizes are very small (of the order of few particles). 16 In this work, particles are observed to merge into clusters quickly at the very beginning of the simulation. After clusters are formed, the main pathway for crystal growth is cluster merging rather than particle attachments from the dilute vapor phase.…”

mentioning

confidence: 82%

“…One immediate unaddressed question is why the BCC-CsCl structure emerges during the early stages of nucleation and ultimately transforms into the FCC-CuAu phase with continued growth. This question becomes especially important because recent studies of analogous 2D systems (both in simulation and experiment) suggest that such transformations are thermodynamically driven, 16,17 which is opposite to the widely acknowledged explanations rooted in the kinetics of nucleation. 24 As a reversible thermodynamic transition should be controllable via an appropriate system variable such as temperature, the potential of such transformations is enormous for the design of reconfigurable materials.…”

mentioning

confidence: 93%

“…While the diffusionless transformations between BCC and FCC are well recognized and important in atomic materials, 10 their existence in selfassembled colloidal systems are less explored. 11,12 Recently, it has been suggested that diffusionless transformations, from BCC-CsCl to FCC-CuAu in 3D 3,13−15 and square to hexagonal in 2D, 16,17 also exist in DNA-functionalized particles (DFPs), 18,19 generating considerable intrigue about the underlying phenomena. The emergence of this behavior in DFPs may result from a unique advantage in the ability to tune interparticle interactions between DFPs by choosing appropriate DNA sequences.…”

mentioning

confidence: 99%

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Temperature-Controlled Reconfigurable Nanoparticle Binary Superlattices

2021

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The presence of diffusionless transformations during the assembly of DNA-functionalized particles (DFPs) is highly significant in designing reconfigurable materials whose structure and functional properties are tunable with controllable variables. In this paper, we first use a variety of computational models and techniques (including free energy methods) to address the nature of such transformations between face-centered cubic (FCC) and body-centered cubic (BCC) structures in a three-dimensional binary system of multiflavored DFPs. We find that the structural rearrangements between BCC and FCC structures are thermodynamically reversible and dependent on crystallite size. Smaller nuclei favor nonclosepacked BCC structures, whereas close-packed FCC structures are observed during the growth stage once the crystallite size exceeds a threshold value. Importantly, we show that a similar reversible transformation between BCC/FCC structures can be driven by changing temperature without introducing additional solution components, highlighting the feasibility of creating reconfigurable crystalline materials. Lastly, we validate this thermally responsive switching behavior in a DFP system with explicit DNA (un)hybridization, demonstrating our findings' applicability to experimentally realizable systems.

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“…1A). Recent studies of crystallization in attractive binary colloidal mixtures (17,18) suggest the possibility of an alternative multistep pathway: that two-step crystallization could proceed via a crystal intermediate that nucleates directly from a gas and then transforms into the final crystal structure by a diffusionless transformation (Fig. 1A).…”

mentioning

confidence: 99%

Two-step crystallization and solid–solid transitions in binary colloidal mixtures

Fang

Hagan

Rogers

2020

Proc. Natl. Acad. Sci. U.S.A.

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Crystallization is fundamental to materials science and is central to a variety of applications, ranging from the fabrication of silicon wafers for microelectronics to the determination of protein structures. The basic picture is that a crystal nucleates from a homogeneous fluid by a spontaneous fluctuation that kicks the system over a single free-energy barrier. However, it is becoming apparent that nucleation is often more complicated than this simple picture and, instead, can proceed via multiple transformations of metastable structures along the pathway to the thermodynamic minimum. In this article, we observe, characterize, and model crystallization pathways using DNA-coated colloids. We use optical microscopy to investigate the crystallization of a binary colloidal mixture with single-particle resolution. We observe classical one-step pathways and nonclassical two-step pathways that proceed via a solid–solid transformation of a crystal intermediate. We also use enhanced sampling to compute the free-energy landscapes corresponding to our experiments and show that both one- and two-step pathways are driven by thermodynamics alone. Specifically, the two-step solid–solid transition is governed by a competition between two different crystal phases with free energies that depend on the crystal size. These results extend our understanding of available pathways to crystallization, by showing that size-dependent thermodynamic forces can produce pathways with multiple crystal phases that interconvert without free-energy barriers and could provide approaches to controlling the self-assembly of materials made from colloids.

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Size-dependent thermodynamic structural selection in colloidal crystallization

Cited by 11 publications

References 30 publications

Hydrodynamic and frictional modulation of deformations in switchable colloidal crystallites

Hydrodynamic and frictional modulation of deformations in switchable colloidal crystallites

Temperature-Controlled Reconfigurable Nanoparticle Binary Superlattices

Two-step crystallization and solid–solid transitions in binary colloidal mixtures

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