Early-stage bifurcation of crystallization in a sphere

Chrameh Fru Mbah, Junwei Wang, Silvan Englisch, Praveen Bommineni, Nydia Roxana Varela-Rosales, Erdmann Spiecker, Nicolas Vogel () and Michael Engel ()
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Chrameh Fru Mbah: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg
Junwei Wang: Friedrich-Alexander-Universität Erlangen-Nürnberg
Silvan Englisch: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg
Praveen Bommineni: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg
Nydia Roxana Varela-Rosales: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg
Erdmann Spiecker: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg
Nicolas Vogel: Friedrich-Alexander-Universität Erlangen-Nürnberg
Michael Engel: IZNF, Friedrich-Alexander-Universität Erlangen-Nürnberg

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Bifurcations in kinetic pathways decide the evolution of a system. An example is crystallization, in which the thermodynamically stable polymorph may not form due to kinetic hindrance. Here, we use confined self-assembly to investigate the interplay of thermodynamics and kinetics in the crystallization pathways of finite clusters. We report the observation of decahedral clusters from colloidal particles in emulsion droplets and show that these decahedral clusters can be thermodynamically stable, just like icosahedral clusters. Our hard sphere simulations reveal how the development of the early nucleus shape passes through a bifurcation that decides the cluster symmetry. A geometric argument explains why decahedral clusters are kinetically hindered and why icosahedral clusters can be dominant even if they are not in the thermodynamic ground state.

Date: 2023
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DOI: 10.1038/s41467-023-41001-6

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