Assembly of clathrates from tetrahedral patchy colloids with narrow patches

Eva G. Noya, Itziar Zubieta, David Pine, Francesco Sciortino

Research output: Contribution to journalArticle

Abstract

Here, we revisit the assembly of colloidal tetrahedral patchy particles. Previous studies have shown that the crystallization of diamond from the fluid phase depends more critically on patch width than on the interaction range: Particles with patches narrower than 40° crystallize readily and those with wide patches form disordered glass states. We find that the crystalline structure formed from the fluid also depends on the patch width. Whereas particles with intermediate patches assemble into diamond (random stacking of cubic and hexagonal diamond layers), particles with narrow patches (with width ≈20° or less) crystallize frequently into clathrates. Free energy calculations show that clathrates are never (in the pressure-temperature plane) thermodynamically more stable than diamond. The assembly of clathrate structures is thus attributed to kinetic factors that originate from the thermodynamic stabilization of pentagonal rings with respect to hexagonal ones as patches become more directional. These pentagonal rings present in the fluid phase assemble into sII clathrate or into large clusters containing 100 particles and exhibiting icosahedral symmetry. These clusters then grow by interpenetration. Still, the organization of these clusters into extended ordered structures was never observed in the simulations.

Original languageEnglish (US)
Article number094502
JournalJournal of Chemical Physics
Volume151
Issue number9
DOIs
StatePublished - Sep 7 2019

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Diamond
clathrates
Colloids
colloids
assembly
diamonds
Fluids
fluids
Crystallization
Free energy
rings
Stabilization
Thermodynamics
Crystalline materials
Glass
stabilization
Kinetics
free energy
crystallization
thermodynamics

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Assembly of clathrates from tetrahedral patchy colloids with narrow patches. / Noya, Eva G.; Zubieta, Itziar; Pine, David; Sciortino, Francesco.

In: Journal of Chemical Physics, Vol. 151, No. 9, 094502, 07.09.2019.

Research output: Contribution to journalArticle

Noya, Eva G. ; Zubieta, Itziar ; Pine, David ; Sciortino, Francesco. / Assembly of clathrates from tetrahedral patchy colloids with narrow patches. In: Journal of Chemical Physics. 2019 ; Vol. 151, No. 9.
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