Neutron scattering study of polyamorphic THF·17(HO) - toward a generalized picture of amorphous states and structures derived from clathrate hydrates

• Published in: Physical chemistry chemical physics : PCCP 2023-05, Vol.25 (21), p.14981-14991
• Main Authors: Brant Carvalho, Paulo H. B, Ivanov, Mikhail, Andersson, Ove, Loerting, Thomas, Bauer, Marion, Tulk, Chris A, Haberl, Bianca, Daemen, Luke L, Molaison, Jamie J, Amann-Winkel, Katrin, Lyubartsev, Alexander P, Bull, Craig L, Funnell, Nicholas P, Häussermann, Ulrich
• Format: Article
• Language: English
• Subjects: Amorphization; Amorphous structure; Chemical bonds; Gas hydrates; Hydration; Hydrogen bonding; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Molecular dynamics; Molecular structure; Neutron scattering; Neutrons; Tetrahydrofuran; Water chemistry
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d3cp00539a

From crystalline tetrahydrofuran clathrate hydrate, THF-CH (THF·17H 2 O, 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·17H 2 O 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 ∼23H 2 O. The local water structure in HDA is reminiscent of pure HDA-ice featuring 5-coordinated H 2 O. In VHDA, the hydration structure of HDA is maintained but the local water structure is densified and resembles pure VHDA-ice with 6-coordinated H 2 O. The hydration structure of THF in RA constitutes ∼18 H 2 O 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. Neutron scattering and simulation unveil amorphous clathrate hydrate structures. THF·17(H 2 O) yields three amorphs under high pressure and low temperature, resembling amorphous ice. THF and water's local structure is shaped by guest-host interactions.