Title: Neutron scattering study of polyamorphic THF·17(H ₂ O) – toward a generalized picture of amorphous states and structures derived from clathrate hydrates

Abstract

From crystalline tetrahydrofuran clathrate hydrate, THF–CH (THF·17H₂O, cubic structure II), three distinct polyamorphs can be derived. First, THF–CH undergoes pressure-induced amorphization when pressurized to 1.3 GPa in the temperature range 77–140 K to a form which, in analogy to pure ice, may be called high-density amorphous (HDA). Second, HDA can be converted to a densified form, VHDA, upon heat-cycling at 1.8 GPa to 180 K. Decompression of VHDA to atmospheric pressure below 130 K produces the third form, recovered amorphous (RA). Results from neutron scattering experiments and molecular dynamics simulations provide a generalized picture of the structure of amorphous THF hydrates with respect to crystalline THF–CH and liquid THF·17H₂O solution (~2.5 M). Although fully amorphous, HDA is heterogeneous with two length scales for water–water correlations (less dense local water structure) and guest–water correlations (denser THF hydration structure). The hydration structure of THF is influenced by guest–host hydrogen bonding. THF molecules maintain a quasiregular array, reminiscent of the crystalline state, and their hydration structure (out to 5 Å) constitutes ~23H₂O. The local water structure in HDA is reminiscent of pure HDA-ice featuring 5-coordinated H₂O. In VHDA, the hydration structure of HDA is maintained but the local water structure is densified andmore » resembles pure VHDA-ice with 6-coordinated H₂O. The hydration structure of THF in RA constitutes ~18 H₂O molecules and the water structure corresponds to a strictly 4-coordinated network, as in the liquid. Both VHDA and RA can be considered as homogeneous.« less

Authors:

Brant Carvalho, Paulo H. B.  ^[1];

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Ivanov, Mikhail  ^[1];

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Andersson, Ove  ^[2];

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Loerting, Thomas  ^[3];

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Bauer, Marion ^[3]; Tulk, Chris A. ^[4]; Haberl, Bianca  ^[4];

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Daemen, Luke L. ^[4]; Molaison, Jamie J.  ^[4];

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Amann-Winkel, Katrin  ^[3];

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Lyubartsev, Alexander P.  ^[1];

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Bull, Craig L.  ^[5];

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Funnell, Nicholas P.  ^[6];

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Häussermann, Ulrich  ^[1]

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+ Show Author Affiliations

1. Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden
2. Department of Physics, Umeå University, SE-90187 Umeå, Sweden
3. Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
4. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
5. ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot, Oxon, OX11 7XN, UK, School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, Scotland, UK
6. ISIS Neutron and Muon Source, Rutherford Appleton Laboratory, Didcot, Oxon, OX11 7XN, UK

Publication Date:

Wed May 31 00:00:00 EDT 2023

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1974663

Alternate Identifier(s):

OSTI ID: 1994623

Grant/Contract Number:  

AC02-06CH11357; AC05-00OR22725

Resource Type:

Published Article

Journal Name:

Physical Chemistry Chemical Physics. PCCP

Additional Journal Information:

Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Volume: 25 Journal Issue: 21; Journal ID: ISSN 1463-9076

Publisher:

Royal Society of Chemistry (RSC)

Country of Publication:

United Kingdom

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY