Cluster Modeling of Network-Forming Amorphization Pathways in AsxS100−x Arsenicals (50 ≤ x ≤ 57) Diven by Nanomilling

Abstract

AbstractComplete hierarchy of network amorphization scenarios initiated in AsxS100-x nanoarsenicals within As4S4-As4S3 cut-Sect. (50 ≤ x ≤ 57) is reconstructed employing materials-computational approach based on ab-initio quantum-chemical modeling code (CINCA). Under nanostructurization due to high-energy mechanical milling, the inter-crystalline transformations to nanoscopic β-As4S4 phase accompanied by appearance of covalent-network amorphous matrix are activated. General amorphization trend under nanomilling obeys tending from molecular cage-like structures to optimally-constrained covalent-bonded networks compositionally invariant with parent arsenical. The contribution of amorphization paths in nanoarsenicals is defined by their chemistry with higher molecular-to-network barriers proper to As4S3-rich alloys. The generated amorphous phase is intrinsically decomposed, possessing double-Tg relaxation due to stoichiometric (x = 40) and non-stoichiometric (x > 40) sub-networks, which are built of AsS3/2 pyramids and As-rich arrangement keeping (i) two separated As-As bonds derived from realgar-type molecules, (ii) two neighboring As-As bonds derived from pararealgar-type molecules or (iii) three neighboring As-As bonds in triangle-like geometry derived from dimorphite-type molecules. Compositional invariance of nanoamorphous phase is ensured by growing sequence of network-forming clusters with average coordination numbers Z in the row (As2S4/2,Z = 2.50) – (As3S5/2, Z = 2.55) – (As3S3/2, Z = 2.67). Diversity of main molecular-to-network amorphizing pathways in nanoarsenicals is reflected on the unified potential energy landscape specified for boundary As4S4 and As4S3 components.