Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6)
Molecular network conformations in the over-stoichiometric arsenoselenides of canonical As<sub>x</sub>Se<sub>100−x</sub> system (40 ≤ x ≤ 100) covering a full row of thioarsenide-type As<sub>4</sub>Se<sub>n</sub> entities (0 ≤ n ≤ 6) are analyzed with...
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| author | Oleh Shpotyuk Malgorzata Hyla Zdenka Lukáčová Bujňáková Yaroslav Shpotyuk Vitaliy Boyko |
| author_facet | Oleh Shpotyuk Malgorzata Hyla Zdenka Lukáčová Bujňáková Yaroslav Shpotyuk Vitaliy Boyko |
| author_sort | Oleh Shpotyuk |
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| description | Molecular network conformations in the over-stoichiometric arsenoselenides of canonical As<sub>x</sub>Se<sub>100−x</sub> system (40 ≤ x ≤ 100) covering a full row of thioarsenide-type As<sub>4</sub>Se<sub>n</sub> entities (0 ≤ n ≤ 6) are analyzed with ab initio quantum-chemical modeling employing cluster-simulation code CINCA. Native (melt-quenching-derived) and nanostructurization-driven (activated by nanomilling) <i>polymorphic</i> and <i>polyamorphic</i> transitions initiated by decomposition of the <i>thioarsenide</i>-type As<sub>4</sub>Se<sub>n</sub> cage molecules and incorporation of their remnants into a newly polymerized arsenoselenide network are identified on the developed map of molecular network clustering in a binary As-Se system. Within this map, compositional counter lines corresponding to preferential molecular or network-forming tendencies in the examined arsenoselenides are determined, explaining that network-crystalline conformations prevail in the boundary compositions corresponding to n = 6 and n = 0, while molecular-crystalline ones dominate inside the rows corresponding to n = 4 and n = 3. A set of primary and secondary equilibrium lines is introduced in the developed clustering map to account for inter-phase equilibria between the most favorable (regular) and competitive (irregular) <i>thioarsenide</i> phases. Straightforward interpretation of decomposition reactions accompanying induced crystallization and amorphization (reamorphization) in the arsenoselenides is achieved, employing disproportionality analysis of <i>thioarsenide</i>-type molecular network conformations within the reconstructed clustering map. The preference of network clustering at the boundaries of the As<sub>4</sub>Se<sub>n</sub> row (at n = 6 and n = 0) disturbs inter-phase equilibria inside this row, leading to unexpected anomalies, such as absence of stable tetra-arsenic triselenide As<sub>4</sub>Se<sub>5</sub> molecular-crystalline species; polyamorphism in mechanoactivated As<sub>4</sub>Se<sub>n</sub> alloys (2 ≤ n ≤ 6); breakdown in the glass-forming ability of melt-quenching-derived arsenoselenides in the vicinity of tetra-arsenic biselenide As<sub>4</sub>Se<sub>2</sub> composition; plastically and normally crystalline polymorphism in tetra-arsenic triselenide As<sub>4</sub>Se<sub>3</sub>-based <i>thioarsenides</i>, and so on. |
| format | Article |
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| spelling | doaj-art-74ab0765f0564a47b54705716ba4e17c2025-08-20T01:50:45ZengMDPI AGMolecules1420-30492025-04-01309196310.3390/molecules30091963Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6)Oleh Shpotyuk0Malgorzata Hyla1Zdenka Lukáčová Bujňáková2Yaroslav Shpotyuk3Vitaliy Boyko4Institute of Physics, Jan Dlugosz University in Częstochowa, 13/15, al. Armii Krajowej, 42-200 Częstochowa, PolandInstitute of Physics, Jan Dlugosz University in Częstochowa, 13/15, al. Armii Krajowej, 42-200 Częstochowa, PolandInstitute of Geotechnics of Slovak Academy of Sciences, 45, Watsonova Str., 04001 Košice, SlovakiaDepartment of Sensor and Semiconductor Electronics, Ivan Franko National University of Lviv, 107, Tarnavskoho Str., 79017 Lviv, UkraineO.G. Vlokh Institute of Physical Optics, Ivan Franko National University of Lviv, 23, Dragomanov Str., 79005 Lviv, UkraineMolecular network conformations in the over-stoichiometric arsenoselenides of canonical As<sub>x</sub>Se<sub>100−x</sub> system (40 ≤ x ≤ 100) covering a full row of thioarsenide-type As<sub>4</sub>Se<sub>n</sub> entities (0 ≤ n ≤ 6) are analyzed with ab initio quantum-chemical modeling employing cluster-simulation code CINCA. Native (melt-quenching-derived) and nanostructurization-driven (activated by nanomilling) <i>polymorphic</i> and <i>polyamorphic</i> transitions initiated by decomposition of the <i>thioarsenide</i>-type As<sub>4</sub>Se<sub>n</sub> cage molecules and incorporation of their remnants into a newly polymerized arsenoselenide network are identified on the developed map of molecular network clustering in a binary As-Se system. Within this map, compositional counter lines corresponding to preferential molecular or network-forming tendencies in the examined arsenoselenides are determined, explaining that network-crystalline conformations prevail in the boundary compositions corresponding to n = 6 and n = 0, while molecular-crystalline ones dominate inside the rows corresponding to n = 4 and n = 3. A set of primary and secondary equilibrium lines is introduced in the developed clustering map to account for inter-phase equilibria between the most favorable (regular) and competitive (irregular) <i>thioarsenide</i> phases. Straightforward interpretation of decomposition reactions accompanying induced crystallization and amorphization (reamorphization) in the arsenoselenides is achieved, employing disproportionality analysis of <i>thioarsenide</i>-type molecular network conformations within the reconstructed clustering map. The preference of network clustering at the boundaries of the As<sub>4</sub>Se<sub>n</sub> row (at n = 6 and n = 0) disturbs inter-phase equilibria inside this row, leading to unexpected anomalies, such as absence of stable tetra-arsenic triselenide As<sub>4</sub>Se<sub>5</sub> molecular-crystalline species; polyamorphism in mechanoactivated As<sub>4</sub>Se<sub>n</sub> alloys (2 ≤ n ≤ 6); breakdown in the glass-forming ability of melt-quenching-derived arsenoselenides in the vicinity of tetra-arsenic biselenide As<sub>4</sub>Se<sub>2</sub> composition; plastically and normally crystalline polymorphism in tetra-arsenic triselenide As<sub>4</sub>Se<sub>3</sub>-based <i>thioarsenides</i>, and so on.https://www.mdpi.com/1420-3049/30/9/1963thioarsenide-type As<sub>4</sub>Se<sub>n</sub> moleculesmolecular network clusteringarsenoselenidesamorphizationcrystallizationpolymorphic transformations |
| spellingShingle | Oleh Shpotyuk Malgorzata Hyla Zdenka Lukáčová Bujňáková Yaroslav Shpotyuk Vitaliy Boyko Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) Molecules thioarsenide-type As<sub>4</sub>Se<sub>n</sub> molecules molecular network clustering arsenoselenides amorphization crystallization polymorphic transformations |
| title | Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) |
| title_full | Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) |
| title_fullStr | Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) |
| title_full_unstemmed | Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) |
| title_short | Diversity of Molecular–Network Conformations in the Over-Stoichiometric Arsenoselenides Covering a Full <i>Thioarsenides</i> Row As<sub>4</sub>Se<sub>n</sub> (0 ≤ <i>n</i> ≤ 6) |
| title_sort | diversity of molecular network conformations in the over stoichiometric arsenoselenides covering a full i thioarsenides i row as sub 4 sub se sub n sub 0 ≤ i n i ≤ 6 |
| topic | thioarsenide-type As<sub>4</sub>Se<sub>n</sub> molecules molecular network clustering arsenoselenides amorphization crystallization polymorphic transformations |
| url | https://www.mdpi.com/1420-3049/30/9/1963 |
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