An Artificial Neural Network Reveals the Nucleation Mechanism of a Binary Colloidal AB(13) Crystal

[Image: see text] Colloidal suspensions of two species have the ability to form binary crystals under certain conditions. The hunt for these functional materials and the countless investigations on their formation process are justified by the plethora of synergetic and collective properties these binary superlattices show. Among the many crystal structures observed over the past decades, the highly exotic colloidal icosahedral AB(13) crystal was predicted to be stable in binary hard-sphere mixtures nearly 30 years ago, yet the kinetic pathway of how homogeneous nucleation occurs in this system is still unknown. Here we investigate binary nucleation of the AB(13) crystal from a binary fluid phase of nearly hard spheres. We calculate the nucleation barrier and nucleation rate as a function of supersaturation and draw a comparison with nucleation of single-component and other binary crystals. To follow the nucleation process, we employ a neural network to identify the AB(13) phase from the binary fluid phase and the competing fcc crystal with single-particle resolution and significant accuracy in the case of bulk phases. We show that AB(13) crystal nucleation proceeds via a coassembly process where large spheres and icosahedral small-sphere clusters simultaneously attach to the nucleus. Our results lend strong support for a classical pathway that is well-described by classical nucleation theory, even though the binary fluid phase is highly structured and exhibits local regions of high bond orientational order.