Mercury Sulfide Dimorphism in Thioarsenate Glasses

M. Kassem; A. Sokolov; A. Cuisset; T. Usuki; S. Khaoulani; P. Masselin; D. Le Coq; J. C. Neuefeind; M. Feygenson; A. C. Hannon; C. J. Benmore; E. Bychkov

doi:10.1021/acs.jpcb.6b03382

Mercury Sulfide Dimorphism in Thioarsenate Glasses

M. Kassem, A. Sokolov, A. Cuisset, T. Usuki, S. Khaoulani, P. Masselin, D. Le Coq, J. C. Neuefeind, M. Feygenson, A. C. Hannon, C. J. Benmore, E. Bychkov

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Abstract

Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As₂S₃. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.). DFT simulations of mercury species and RMC modeling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS_2/2)_m oligomeric chains (1 ≤ m ≤ 6) are acting as a network former while the HgS_4/4-related mixed agglomerated units behave as a modifier.

Original language	English
Pages (from-to)	5278-5290
Number of pages	13
Journal	Journal of Physical Chemistry B
Volume	120
Issue number	23
DOIs	https://doi.org/10.1021/acs.jpcb.6b03382
State	Published - Jun 16 2016

Funding

This work was supported by Agence Nationale de la Recherche (ANR, France) under Grant No. ANR-15-ASTR-0016-01. Research conducted at ORNLs Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime allocation (RB1510269) from the Science and Technology Facilities Council. Work at the Advanced Photon Source, Argonne National Laboratory, was supported in part by the Office of Basic Energy Sciences, U.S. Department of Energy, under Contract No. DE-AC02-06CH1135.

Funders	Funder number
ISIS	RB1510269
Office of Basic Energy Sciences
Scientific User Facilities Division
U.S. Department of Energy
Argonne National Laboratory	DE-AC02-06CH1135
Advanced Photon Sciences
Science and Technology Facilities Council
Agence Nationale de la Recherche	ANR-15-ASTR-0016-01

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title = "Mercury Sulfide Dimorphism in Thioarsenate Glasses",

abstract = "Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As2S3. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.). DFT simulations of mercury species and RMC modeling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS2/2)m oligomeric chains (1 ≤ m ≤ 6) are acting as a network former while the HgS4/4-related mixed agglomerated units behave as a modifier.",

author = "M. Kassem and A. Sokolov and A. Cuisset and T. Usuki and S. Khaoulani and P. Masselin and {Le Coq}, D. and Neuefeind, {J. C.} and M. Feygenson and Hannon, {A. C.} and Benmore, {C. J.} and E. Bychkov",

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AU - Kassem, M.

AU - Sokolov, A.

AU - Cuisset, A.

AU - Usuki, T.

AU - Khaoulani, S.

AU - Masselin, P.

AU - Le Coq, D.

AU - Neuefeind, J. C.

AU - Feygenson, M.

AU - Hannon, A. C.

AU - Benmore, C. J.

AU - Bychkov, E.

PY - 2016/6/16

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N2 - Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As2S3. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.). DFT simulations of mercury species and RMC modeling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS2/2)m oligomeric chains (1 ≤ m ≤ 6) are acting as a network former while the HgS4/4-related mixed agglomerated units behave as a modifier.

AB - Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As2S3. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.). DFT simulations of mercury species and RMC modeling of high-resolution diffraction data provide additional details on local Hg environment and connectivity implying the (HgS2/2)m oligomeric chains (1 ≤ m ≤ 6) are acting as a network former while the HgS4/4-related mixed agglomerated units behave as a modifier.

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Mercury Sulfide Dimorphism in Thioarsenate Glasses

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