Ab initio quantum chemical investigation of arsenic sulfide molecular diversity from As4S6 and As4

Kyono, Atsushi

doi:10.1007/s00269-013-0607-3

Cited by 12 publications

(6 citation statements)

References 30 publications

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“…Moreover, arsenolite's bulk modulus is in the range of the softest molecular crystals [24,[31][32][33][34] and smaller than related molecular solids, like minerals realgar (α-As 4 S 4 , B 0 = 8.1 GPa, and B 0 = 9.0) [33] and pararealgar (β-As 4 S 4 , B 0 = 10.9 GPa, and B 0 = 8.9) [34]. These similar compounds [35] have a cagelike structure based on As tetrahedra (Fig. 1, left) surrounded by anions in a closed-compact configuration.…”

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confidence: 90%

Ordered helium trapping and bonding in compressed arsenolite: Synthesis ofAs4O6·2He

et al. 2016

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Compression of arsenolite has been studied from a joint experimental and theoretical point of view. Experiments on this molecular solid at high pressures with different pressure-transmitting media have been interpreted thanks to state-of-the-art ab initio calculations. Our results confirm arsenolite as one of the most compressible minerals and provide evidence for ordered helium trapping above 3 GPa between adamantane-type As 4 O 6 cages. Our calculations indicate that, at relatively small pressures, helium establishes rather localized structural bonds with arsenic forming a compound with stoichiometry As 4 O 6 · 2He. All properties of As 4 O 6 · 2He are different from those of parent As 4 O 6 . In particular, pressure-induced amorphization, which occurs in arsenolite above 15 GPa, is impeded in As 4 O 6 · 2He, thus resulting in a mechanical stability of As 4 O 6 · 2He beyond 30 GPa. Our work paves the way to explore the formation of alternative compounds by pressure-induced trapping and reaction of gases, small atomic or molecular species, in the voids of molecular solids containing active lone electron pairs. DOI: 10.1103/PhysRevB.93.054102Molecular solids are very soft materials with openframework structures composed of molecular units, exhibiting strong covalent interatomic forces, which are linked by weak intermolecular forces, such as van der Waals interactions or hydrogen bonding forces. Pressure is a thermodynamic variable that allows tuning interatomic distances and consequently is a powerful tool to study atomic interactions and the connectivity of different molecular units -hence, the possibility of molecular solids to trap small atoms or molecules. In this sense, molecule trapping has received a lot of interest from the scientific community due to its potential industrial applications covering hydrogen storage [1] and CO 2 segregation from other organic compounds [2], among others. Recently, the small size of helium has triggered the study of pressure-induced helium trapping and how this effect affects the compressibility of host compounds. Those first studies were focused on helium trapping in silica glass [3][4][5] that is an amorphous compound with disordered interstitial voids large enough to host and trap helium. However, more studies need to be made of pressure-induced helium trapping in ordered crystallographic compounds, such as molecular solids.Helium reaction is a challenge since it is one of the most inert elements in nature [6]. Previous studies of helium trapping in glasses have not revealed the pressure-induced reactivity of helium with the glass structure. On the search of the formation of solid structures with helium, the study of * juasant2@upv.es † fjmanjon@upv.es mixtures of helium with other noble gases at high pressures has exhibited successful results. The mix of those fluids under pressure allows the formation of solid van der Waals compounds with exotic stoichiometries [7,8] [He(N 2 ) 11 , Ne(He) 2 ] given by the solubility of helium and dominated by the crystallization proces...

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confidence: 90%

Ordered helium trapping and bonding in compressed arsenolite: Synthesis ofAs4O6·2He

et al. 2016

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“…Séréna, Alpes-Maritimes, France) in association with native arsenic and realgar. The structure has been studied in detail by Kyono (2013) and Bonazzi et al (2016). The former hypothesized As 4 S molecular geometry while the latter demonstrated a layered structure that "consists of an alternated stacking along the [010] axis of two kinds of corrugated layers which match the As 2 and As 2 S composition, respectively" (Bonazzi et al 2016).…”

Section: Orpiment and Anorpiment (As 2 S 3 )mentioning

confidence: 99%

Pigments—Arsenic-based yellows and reds

Gliozzo

Burgio

2021

Archaeol Anthropol Sci

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This review offers an update on arsenic-bearing minerals and pigments with the aim of serving as a guide for the study of Cultural Heritage materials in which these materials can be found.The different As-bearing mineral phases (realgar, pararealgar, orpiment, anorpiment, alacranite, dimorphite, bonazziite, uzonite, wakabayashilite, duranusite, arsenolite and claudetite) and some of their light-induced products are examined. The occurrence of As-sulfides and their trade, use, alteration and degradation are also reviewed. Finally, the analytical techniques commonly used for the identification of arsenic-containing pigments are discussed. The manuscript concludes with a good-practice guide and a summary of key concepts for use by those working in the field of cultural heritage.

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“…Pararealgar As 4 S 4 as metastable product of light-induced alteration from both tetra-arsenic tetrasulphide polymorphs (a-As 4 S 4 and b-As 4 S 4 ) [8,41,42], was found to exist (albeit in small amount) in As 4 S 4 -As 4 S 3 alloys prepared by melt-quenching and/or nanomilling [20] (following the Kyono's notation [43], and for sake of convenience, this phase will be marked thereafter as p-As 4 S 4 ).…”

Section: Cluster Modeling Of Amorphization Scenarios Activated From Pararealgar As 4 S 4 Phasementioning

confidence: 99%

“…refs. [8,14] derived from ab-initio quantum-chemical model of Kyono [43]. However, the energetic specificity of competitive molecular-network amorphizing tendencies in dimorphitetype As 4 S 3 arsenicals has not been established.…”

Section: Cluster Modeling Of Amorphization Scenarios Activated From Pararealgar As 4 S 4 Phasementioning

confidence: 99%

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

et al. 2021

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Complete 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.

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Ab initio quantum chemical investigation of arsenic sulfide molecular diversity from As4S6 and As4

Cited by 12 publications

References 30 publications

Ordered helium trapping and bonding in compressed arsenolite: Synthesis ofAs4O6·2He

Ordered helium trapping and bonding in compressed arsenolite: Synthesis ofAs4O6·2He

Pigments—Arsenic-based yellows and reds

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

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