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Elucidating the guest disorder in structure II argon hydrate - A neutron diffraction isotopic substitution study
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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Number of Authors: 62020 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 285, article id 121220Article in journal (Refereed) Published
Abstract [en]

Clathrate hydrates with the cubic structure II (CS-II) form typically with large guest molecules, such as tetrahydrofuran, trimethylamine oxide, or propane. However, CS-II is also realized for argon hydrate despite the comparatively small van der Waals diameter of the guest (around 3.8 angstrom). Here, the structure of deuterated argon hydrate was studied at ambient pressure in the temperature range 20-95 K using neutron diffraction and comparing natural Ar with Ar-36, which scatters neutrons more than 13 times more efficiently. The procedure allowed to unambiguously establish the positional disorder within the large cages of CS-H, while simultaneously refining host and guest structures. These cages are singly occupied and off-centered argon atoms distribute on two tetrahedron-shaped split positions with a ratio 3:1. Molecular dynamics (MD) simulations revealed that the crystallographic positional disorder structure is due to mobile argon atoms even at 20 K. The MD potential energy distribution confirmed the diffraction model. It is noted that the unit cell volumes of argon hydrate in the investigated temperature range are virtually identical to N-2 hydrate, which has a similar composition at ambient pressure, indicating a very similar (slightly attractive) host-guest interaction.

Place, publisher, year, edition, pages
2020. Vol. 285, article id 121220
Keywords [en]
Clathrate hydrates, Disorder, Neutron diffraction
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-181309DOI: 10.1016/j.jssc.2020.121220ISI: 000521107900003OAI: oai:DiVA.org:su-181309DiVA, id: diva2:1431665
Available from: 2020-05-24 Created: 2020-05-24 Last updated: 2023-02-03Bibliographically approved
In thesis
1. Pressure-Induced Amorphization and Distinct Amorphous States of Clathrate Hydrates
Open this publication in new window or tab >>Pressure-Induced Amorphization and Distinct Amorphous States of Clathrate Hydrates
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis summarizes a study on the pressure-induced amorphization (PIA) and structures of amorphous states of clathrate hydrates (CHs).

PIA involves the transition of a crystalline material into an amorphous solid in response of mechanical compression at temperatures well below the melting point. The first material observed to undergo PIA was hexagonal ice. More recently it was shown that compounds of water undergo the same phenomenon without decomposition, despite the presence of solutes. CHs, which are crystalline inclusion compounds consisting of water molecules encaging small guest species, undergo PIA at ca. 1–4 GPa below 145 K. The obtained amorphous CH phase can be further densified on isobaric heating at high pressure. This annealing step enables to retain an amorphous material on pressure release. There has been a significant amount of studies into the understanding of the nature of PIA and transformations between amorphous phases of pure ice. The aim of this thesis has been the understanding of the PIA in CHs and its relation to pure ice. New information on the nature of PIA and subsequent amorphous-amorphous transitions in CH systems were gained from structural studies and in situ neutron diffraction played pivotal role due to the sensitivity of neutrons to the light element hydrogen. Here a generalized understanding of the PIA in CHs and a clear image of amorphous CH structures are presented.

Abstract [sv]

Denna avhandling sammanfattar en studie om tryckinducerad amorfisering (TIA) av klatrathydrater (KH), samt strukturer av amorfa tillstånd där av.

TIA är övergången av ett kristallint material till ett amorft fast ämne som svar på mekanisk kompression vid temperaturer långt under smältpunkten. Det första materialet som observerades genomgå TIA var hexagonal is. Därefter har det visat sig att det finns strukturer av vatten som trots närvaron av lösta ämnen genomgår samma fenomen utan att strukturen bryts ned. KH:er är kristallina inneslutningskomplex som består av ett gitter av vattenmolekyler, vilka omsluter små gästmolekyler. Dessa strukturer genomgår TIA vid ca. 1–4 GPa vid temperaturer under 145 K. Den erhållna amorfa KH-fasen kan förtätas ytterligare vid isobarisk uppvärmning under högt tryck. Detta steg gör det möjligt att behålla ett amorft material vid tryckavlastning. Det har gjorts en betydande mängd studier av TIA:s natur och omvandlingar mellan amorfa faser av ren is. Syftet med denna avhandling har varit att förstå TIA i KH:er och dess relation till ren is. Ny information om karaktären hos TIA och efterföljande amorfa-amorfa övergångar i KH-system erhölls från strukturella studier, där in situ neutrondiffraktion spelade en avgörande roll tack vare neutronernas känslighet för det lätta elementet väte. Utifrån detta arbete presenteras här en generaliserad förståelse av TIA i KH samt en tydlig bild av amorfa KH-strukturer.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2023. p. 78
Keywords
Clathrate Hydrates, Pressure-Induced Amorphization, Amorphous States, Glassy States, Ice, Neutron Diffraction, Klatrathydrater, Tryckinducerad Amorfisering, Amorfa tillstånd, Glasartade tillstånd, Is, Neutrondiffraktion
National Category
Condensed Matter Physics Materials Chemistry
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:su:diva-214449 (URN)978-91-8014-186-4 (ISBN)978-91-8014-187-1 (ISBN)
Public defence
2023-03-31, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2023-03-08 Created: 2023-02-03 Last updated: 2023-03-01Bibliographically approved

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B. Brant Carvalho, Paulo H.Häussermann, Ulrich

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