Cluster modeling of nanostructurization-driven reamorphization pathways in glassy arsenoselenides: a case study of arsenic monoselenide g-AsSe

Nanostructurization-driven reamorphization pathways in glassy arsenic monoselenide g-AsSe originated from both realgar- and pararealgar-type As4Se4 molecules are refined employing ab initio quantum-chemical modeling with atomic cluster-simulation code CINCA. At the basis of calculated cluster-forming energies, most possible molecular-to-network disproportionality scenarios are identified in g-AsSe and parameterized in terms of potential energy landscape. The global equilibrium in melt-quenched g-AsSe is shown to be shifted to under-constrained molecular entities of realgar- and pararealgar-type, supplemented by some network-forming derivatives like optimally-constrained single-broken realgar-type clusters. As a result, the glassy network of melt-quenched g-AsSe tends to be more topologically perfect keeping as many as possible small-ring entities. On the contrary, under externally induced nanostructurization activated by nanomilling, the global equilibrium is shifted to over-constrained reamorphized network built of chain-like entities without small rings stabilized with nearly the same molecular-to-network disproportionality barrier approaching ~ 0.30 kcal/mol.