Elucidation of the pressure induced amorphization of tetrahydrofuran clathrate hydrate

PHBB Carvalho and A Mace and CL Bull and NP Funnell and CA Tulk and O Andersson and U Haussermann, JOURNAL OF CHEMICAL PHYSICS, 150, 204506 (2019).

DOI: 10.1063/1.5083958

The type II clathrate hydrate (CH) THF center dot 17 H2O (THF = tetrahydrofuran) is known to amorphize on pressurization to similar to 1.3 GPa in the temperature range 77-140 K. This seems to be related to the pressure induced amorphization (PIA) of hexagonal ice to high density amorphous (HDA) ice. Here, we probe the PIA of THF-d(8)center dot 17 D2O (TDF-CD) at 130 K by in situ thermal conductivity and neutron diffraction experiments. Both methods reveal amorphization of TDF-CD between 1.1 and 1.2 GPa and densification of the amorphous state on subsequent heating from 130 to 170 K. The densification is similar to the transition of HDA to very-high-density-amorphous ice. The first diffraction peak (FDP) of the neutron structure factor function, S(Q), of amorphous TDF-CD at 130 K appeared split. This feature is considered a general phenomenon of the crystalline to amorphous transition of CHs and reflects different length scales for D-D and D-O correlations in the water network and the cavity structure around the guest. The maximum corresponding to water-water correlations relates to the position of the FDP of HDA ice at similar to 1 GPa. Upon annealing, the different length scales for water-water and water-guest correlations equalize and the FDP in the S(Q) of the annealed amorph represents a single peak. The similarity of local water structures in amorphous CHs and amorphous ices at in situ conditions is confirmed from molecular dynamics simulations. In addition, these simulations show that THF guest molecules are immobilized and retain long-range correlations as in the crystal. (C) 2019 Author(s).

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