A theory of entropic bonding

Vo, Thi; Glotzer, Sharon C.

doi:10.1073/pnas.2116414119

Cited by 32 publications

(30 citation statements)

References 57 publications

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“…4 ). We show that icosahedral clusters of hard TTs have twice the fluid-solid interfacial free-energy (or entropy) compared to icosahedral clusters of hard spheres as a natural consequence of stronger entropic bonding 25 in the former system. Our study isolates the essential role of surface tension in stabilizing the inherently strained icosahedral twinned cluster in a dense fluid, and suggests approaches for engineering the surface tension.…”

Section: Introductionmentioning

confidence: 87%

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Lee

Glotzer

2022

Nat Commun

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Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

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Section: Introductionmentioning

confidence: 87%

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Lee

Glotzer

2022

Nat Commun

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“…The separation of driving forces for a generic chemical mechanism into their energetic and entropic components has been a topic of continued interest over the decades. This is relevant to diverse problems such as solute aggregation, , drug and ligand binding to proteins , and other biomolecules, , nucleation, , molecular permeation through membranes,; − and numerous phase transitions. − This separation provides fundamental insight into the natures of interactions that stabilize or destabilize a given material and can guide further design strategies.…”

Section: Introductionmentioning

confidence: 99%

Quantifying Energetic and Entropic Pathways in Molecular Systems

2022

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When examining dynamics occurring at nonzero temperatures, both energy and entropy must be taken into account to describe activated barrier crossing events. Furthermore, good reaction coordinates need to be constructed to describe different metastable states and the transition mechanisms between them.Here we use a physics-based machine learning method called state predictive information bottleneck (SPIB) to find nonlinear reaction coordinates for three systems of varying complexity. SPIB is able to correctly predict an entropic bottleneck for an analytical flat-energy double-well system and identify the entropyand energy-dominated pathways for an analytical four-well system. Finally, for a simulation of benzoic acid permeation through a lipid bilayer, SPIB is able to discover the entropic and energetic barriers to the permeation process. Given these results, we thus establish that SPIB is a reasonable and robust method for finding the important entropy, energy, and enthalpy barriers in physical systems, which can then be used to enhance the understanding and sampling of different activated mechanisms.

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“…The separation of driving forces for a generic chemical mechanism into its energetic and entropic components has been a topic of continued interest over the decades. This is relevant to diverse problems such as solute aggregation, 1,2 ; drug, ligand binding to proteins 3,4 and other biomolecules 5,6 ; nucleation 7,8 ; molecular permeation through membranes [9][10][11] ; and entropy-driven phase transitions [12][13][14][15] . This separation gives fundamental insight into the nature of interactions stabilizing or destabilizing a given material, and can guide further design strategies.…”

Section: Introductionmentioning

confidence: 99%

Quantifying Energetic and Entropic Pathways in Molecular Systems

Beyerle¹,

Shams²,

Tiwary³

2022

Preprint

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When examining dynamics occurring at non-zero temperatures, both energy and entropy must be taken into account while describing activated barrier crossing events. Furthermore, good reaction coordinates need to be constructed to describe different metastable states and the transition mechanisms between them. Here we use a physics-based machine learning method called the State Predictive Information Bottleneck (SPIB) to find non-linear reaction coordinates for three systems of varying complexity. The SPIB is able to predict correctly an entropic bottleneck for an analytical flat-energy double-well system and identify the entropyand energy-dominated pathways for an analytical four-well system. Finally, for a simulation of benzoic acid permeation through a lipid bilayer, SPIB is able to discover the the entropic and energetic barriers to the permeation process. Given these results, we thus establish that SPIB is a reasonable and robust method for finding the important entropy and energy/enthalpy barriers in physical systems, which can then be used for enhanced understanding and sampling of different activated mechanisms.

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A theory of entropic bonding

Cited by 32 publications

References 57 publications

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Quantifying Energetic and Entropic Pathways in Molecular Systems

Quantifying Energetic and Entropic Pathways in Molecular Systems

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