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

• Published in: Journal of nanoparticle research : an interdisciplinary forum for nanoscale science and technology Vol. 24; no. 3
• Main Authors: Shpotyuk, O., Hyla, M., Boyko, V., Shpotyuk, Y., Balitska, V.
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Netherlands 01.03.2022; Springer Nature B.V
• Subjects: Arsenic; Characterization and Evaluation of Materials; Chemistry and Materials Science; Clusters; Inorganic Chemistry; Lasers; Materials Science; Modelling; Nanoparticles; Nanotechnology; Optical Devices; Optics; Photonics; Physical Chemistry; Potential energy; Quantum chemistry; Quenching; Research Paper; Rings (mathematics); Nanostructurization; Arsenic monoselenide; Reamorphization; Nanomilling
• ISSN: 1388-0764; 1572-896X
• DOI: 10.1007/s11051-022-05447-x

Nanostructurization-driven reamorphization pathways in glassy arsenic monoselenide g-AsSe originated from both realgar- and pararealgar-type As 4 Se 4 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.