Medium-Range Structural Order in Amorphous Arsenic

Medium-range order (MRO) is a key structural feature of amorphous materials, but its origin and nature remain elusive. Here, we reveal the MRO in amorphous arsenic (<i>a</i>-As) using advanced atomistic simulations, based on machine-learned potentials derived using automated workflows. Our simulations accurately reproduce the experimental structure factor of <i>a</i>-As, especially the first sharp diffraction peak (FSDP), which is a signature of MRO. We compare and contrast the structure of <i>a</i>-As with that of its lighter homologue, red amorphous phosphorus (<i>a</i>-P): we find that <i>a</i>-As has a more uniform dihedral-angle distribution, and so we confirm that its structure can be thought of as a 3-fold coordinated continuous random network in first approximation, in contrast to the more molecular-cluster-like structure of <i>a</i>-P. The pressure-dependent structural behaviors of <i>a</i>-As and <i>a</i>-P differ as well, and the origin of the FSDP is closely correlated with the size and spatial distribution of voids in the amorphous networks. Our work provides fundamental insights into MRO in an amorphous elemental system, and more widely it illustrates the usefulness of automation for machine-learning-driven atomistic simulations.