87 research outputs found
New mineralogy of the outer solar system and the high-pressure behaviour of methane
This thesis will introduce the study of methane as a mineral. Along with ammonia and
water, methane is one of the main planetary-forming materials in the outer solar system.
The topic of `new mineralogy of the outer solar system' is outlined and introduced,
and previous studies in the area are discussed. This review identities a lack of highpressure
structural knowledge on methane when compared to ammonia and water.
The significance of this knowledge for the study of the planets Neptune and Uranus is
discussed.
The crystal structures of methane above 5.2 GPa were, prior to this thesis, unknown.
To tackle this long-standing problem an integrated approach of high-pressure diffraction
techniques had to be used. The dominance of hydrogen within the structures of methane
necessitated the use of neutron diffraction. The difficulties and limitations of highpressure
neutron powder diffraction are presented. It will be shown that the complexity
of the subsequent structures required the use of single-crystal x-ray diffraction. Using
a combination of x-ray and neutron diffraction the structures of methane phase A (5.2
- 10 GPa) and B (10 - 25 GPa) were solved.
The structure of phase A, was shown to conform to an indexing from literature
[Nakahata 99] of a rhombohedral unit cell with α ≈ 89.3° and a ≈ 8.6 Å. Powder data
were insufficient to determine atomic positions for this phase, and a single-crystal xray
diffraction study was undertaken. The process of growing samples for this study
is described as well as data collection. As a result of these studies the carbon atoms
were located within methane phase A, and the density of the structure confined. The
heavy atom structure, of phase A, was refined against neutron powder diffraction data,
enabling positions of hydrogen atoms to be found.
Preliminary powder diffraction studies of methane phase B found that the structure
did not conform to the unit cell described within the literature. The phase was instead
assigned to a cubic unit cell with a ≈ 11.73 Å. Similarly to the studies of phase A,
a single-crystal x-ray diffraction study was undertaken. This was complicated by the
presence of a contaminant within the sample area. This contaminant was shown to
have no effect on the structural results. From a single-crystal study the heavy atom structure of phase B was found. The thesis charts the attempt, but ultimate failure,
to obtain neutron powder diffraction on this phase. Comparisons of phase B with the
higher pressure phase HP (25 GPa +) led to the conclusion that there would still be
some disorder within the hydrogen atoms of phase B.
Other studies have been carried out on the methane phase diagram. A Raman
spectroscopy study, in the literature, on the low-temperature and high-pressure region
of the phase diagrams (20 K up to 30 GPa) had suggested the existence of 3 additional
phases of methane. A low-temperature, high-pressure neutron diffraction experiment
was undertaken to try and characterise these phases. It was found that the phase A
structure persisted under all conditions (to 20 K and 5 GPa) throwing the original
results into question. During the growth of single-crystals for the above studies on
phase A and B, a high-temperature solid-solid phase transition was observed. This
transition line was mapped out and the phase resulting from it characterised with
high-temperature single-crystal x-ray diffraction
Neutron powder diffraction study on the iron-based nitride superconductor ThFeAsN
We report neutron diffraction and transport results on the newly discovered
superconducting nitride ThFeAsN with 30 K. No magnetic transition, but a
weak structural distortion around 160 K, is observed cooling from 300 K to 6 K.
Analysis on the resistivity, Hall transport and crystal structure suggests this
material behaves as an electron optimally doped pnictide superconductors due to
extra electrons from nitrogen deficiency or oxygen occupancy at the nitrogen
site, which together with the low arsenic height may enhance the electron
itinerancy and reduce the electron correlations, thus suppress the static
magnetic order.Comment: 4 pages, 4 figures, Accepted by EP
Use of a miniature diamond-anvil cell in a joint X-ray and neutron high-pressure study on copper sulfate pentahydrate
Single-crystal X-ray and neutron diffraction data are usually collected using separate samples. This is a disadvantage when the sample is studied at high pressure because it is very difficult to achieve exactly the same pressure in two separate experiments, especially if the neutron data are collected using Laue methods where precise absolute values of the unit-cell dimensions cannot be measured to check how close the pressures are. In this study, diffraction data have been collected under the same conditions on the same sample of copper(II) sulfate pentahydrate, using a conventional laboratory diffractometer and source for the X-ray measurements and the Koala single-crystal Laue diffractometer at the ANSTO facility for the neutron measurements. The sample, of dimensions 0.40 × 0.22 × 0.20 mm(3) and held at a pressure of 0.71 GPa, was contained in a miniature Merrill–Bassett diamond-anvil cell. The highly penetrating diffracted neutron beams passing through the metal body of the miniature cell as well as through the diamonds yielded data suitable for structure refinement, and compensated for the low completeness of the X-ray measurements, which was only 24% on account of the triclinic symmetry of the sample and the shading of reciprocal space by the cell. The two data-sets were combined in a single ‘XN’ structure refinement in which all atoms, including H atoms, were refined with anisotropic displacement parameters. The precision of the structural parameters was improved by a factor of up to 50% in the XN refinement compared with refinements using the X-ray or neutron data separately
Accurate H-atom parameters for the two polymorphs of L-histidine at 5, 105 and 295 K
The crystal structure of the monoclinic polymorph of the primary amino acid l-histidine has been determined for the first time by single-crystal neutron diffraction, while that of the orthorhombic polymorph has been reinvestigated with an untwinned crystal, improving the experimental precision and accuracy. For each polymorph, neutron diffraction data were collected at 5, 105 and 295 K. Single-crystal X-ray diffraction experiments were also performed at the same temperatures. The two polymorphs, whose crystal packing is interpreted by intermolecular interaction energies calculated using the Pixel method, show differences in the energy and geometry of the hydrogen bond formed along the c direction. Taking advantage of the X-ray diffraction data collected at 5 K, the precision and accuracy of the new Hirshfeld atom refinement method implemented in NoSpherA2 were probed choosing various settings of the functionals and basis sets, together with the use of explicit clusters of molecules and enhanced rigid-body restraints for H atoms. Equivalent atomic coordinates and anisotropic displacement parameters were compared and found to agree well with those obtained from the corresponding neutron structural models
The crystal structure of methane B at 8 GPa-An alpha-Mn arrangement of molecules
From a combination of powder and single-crystal synchrotron x-ray diffraction data we have determined the carbon substructure of phase B of methane at a pressure of ∼8 GPa. We find this substructure to be cubic with space group I4 ¯ 3m
I4¯3m
and 58 molecules in the unit cell. The unit cell has a lattice parameter a = 11.911(1) Å at 8.3(2) GPa, which is a factor of √2 larger than had previously been proposed by Umemoto et al. [J. Phys.: Condens. Matter14, 10675 (2002)]. The substructure as now solved is not related to any close-packed arrangement, contrary to previous proposals. Surprisingly, the arrangement of the carbon atoms is isostructural with that of α-manganese at ambient conditions. © 2014, AIP Publishing LLC
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