Complete hierarchy of network amorphization scenarios initiated in As_xS_100-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-T_g relaxation due to stoichiometric (x = 40) and non-stoichiometric (x > 40) sub-networks, which are built of AsS_3/2 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 (As₂S_4/2, Z = 2.50) – (As₃S_5/2, Z = 2.55) – (As₃S_3/2, 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.

在作为发起网络非晶化方案的完整层次_X小号_100-X内。如nanoarsenicals ₄小号₄ -As ₄ š ₃切口教。（50≤x≤57）是基于从头算量子化学建模代码（CINCA）的材料计算方法重建的。下由于高能量的机械研磨nanostructurization，帧间结晶转变至β纳米-作为₄小号₄伴随共价网络无定形基质出现的相被激活。纳米铣削下的总体非晶化趋势遵循从分子笼状结构到组成受母砷不变的最佳约束共价键网络的趋势。纳米砷中非晶化路径的贡献是由其化学性质以及富含As ₄ S _3的合金所具有的较高的分子-网络壁垒来定义的。生成的非晶相本质上分解，由于化学计量比（x = 40）和非化学计量比（x> 40）子网络（由AsS _3/2建立），具有两倍的T _g弛豫。金字塔和富As排列，保持（i）源自雄黄型分子的两个分离的As-As键，（ii）源自准雄黄型分子的两个相邻的As-As键，或（iii）三角形中的三个相邻的As-As键类晶形衍生自双晶石型分子。纳米非晶相的组成不变性是通过在该行中形成具有平均配位数Z（As ₂ S _{4/ 2 ，}Z  = 2.50）的网络形成簇的序列来确保的–（As ₃ S _5/2，Z  = 2.55）–（作为₃ S _3/2，Z = 2.67）。纳米砷中主要分子到网络的非晶化途径的多样性反映在针对边界As ₄ S ₄和As ₄ S ₃组分规定的统一势能图上。