Crystal Structure of Moganite and Its Anisotropic Atomic Displacement Parameters Determined by Synchrotron X-ray Diffraction and X-ray/Neutron Pair Distribution Function Analyses

The crystal structure of moganite from the Mogán formation on Gran Canaria has been re-investigated using high-resolution synchrotron X-ray diffraction (XRD) and X-ray/neutron pair distribution function (PDF) analyses. Our study for the first time reports the anisotropic atomic displacement parameters (ADPs) of a natural moganite. Rietveld analysis of synchrotron XRD data determined the crystal structure of moganite with the space group I2/a. The refined unit-cell parameters are a = 8.7363(8), b = 4.8688(5), c = 10.7203(9) Å, and β = 90.212(4)°. The ADPs of Si and O in moganite were obtained from X-ray and neutron PDF analyses. The shapes and orientations of the anisotropic ellipsoids determined from X-ray and neutron measurements are similar. The anisotropic ellipsoids for O extend along planes perpendicular to the Si-Si axis of corner-sharing SiO4 tetrahedra, suggesting precession-like movement. Neutron PDF result confirms the occurrence of OH over some of the tetrahedral sites. We postulate that moganite nanomineral is stable with respect to quartz in hypersaline water. The ADPs of moganite show a similar trend as those of quartz determined by single-crystal XRD. In short, the combined methods can provide high-quality structural parameters of moganite nanomineral, including its ADPs and extra OH position at the surface. This approach can be used as an alternative means for solving the structures of crystals that are not large enough for single-crystal XRD measurements, such as fine-grained and nanocrystalline minerals formed in various geological environments.

Nematic fluctuations in iron-oxychalcogenide Mott insulators

Nematic fluctuations occur in a wide range physical systems from biological molecules to cuprates and iron pnictide high-Tc superconductors. It is unclear whether nematicity in pnictides arises from electronic spin or orbital degrees of freedom. We studied the iron-based Mott insulators La2O2Fe2OM2M = (S, Se), which are structurally similar to pnictides. Nuclear magnetic resonance revealed a critical slowing down of nematic fluctuations and complementary Mössbauerr spectroscopy data showed a change of electrical field gradient. The neutron pair distribution function technique detected local C2 fluctuations while neutron diffraction indicates that global C4 symmetry is preserved. A geometrically frustrated Heisenberg model with biquadratic and single-ion anisotropic terms provides the interpretation of the low temperature magnetic fluctuations. The nematicity is not due to spontaneous orbital order, instead it is linked to geometrically frustrated magnetism based on orbital selectivity. This study highlights the interplay between orbital order and spin fluctuations in nematicity.

Quantum Algebraic Description of the Pairing Correlations in a Single-j Nuclear Shell

Pairing in a single-j shell is described in terms of two Q-oscillators, one describing the J=0 fermion pairs and the other corresponding to the J≠0 pairs, the deformation parameter Τ = lnQ being related to the inverse of the size of the shell. Using these two oscillators an SUQ(2) algebra is constructed, while a pairing Hamiltonian giving the correct energy eigenvalues up to terms of first order in the small parameter can be written in terms of the Casimir operators of the algebras appearing in the UQ(2) > UQ(1) chain, thus exhibiting a quantum algebraic dynamical symmetry. The additional terms introduced by the Q-oscillator are found to improve the agreement with the experimental data for the neutron pair separation energies of the Sn isotopes, with no extra parameter introduced.

Metal Oxide Decorated Porous Carbons from Controlled Calcination of a Metal-Organic Framework

Thermal decomposition of an iron-based MOF was conducted under controlled gas environments to understand the resulting porous carbon structure. Different phases and crystallite sizes of iron oxide are produced based on the specific gas species. In particular, air results in iron(III) oxide, and D₂O and CO₂ results in the mixed valent iron (II,III) oxide. Performing the carbonization under non-oxidative or reducing conditions (N₂, He, H₂) results in the formation of a mixture of both iron (II,III) oxide and iron (III) oxide. Based on in situ and air free handling experiments, it was observed that this is partially due to the formation of zero-valent iron metal that is rapidly oxidized when exposed to air. Neutron pair distribution function analysis provided insight into the effect of the gas environment on the local structure of the porous carbon, indicating a noticeable change in local order between the D₂O and the N₂ calcined samples.

Metal Oxide Decorated Porous Carbons from Controlled Calcination of a Metal-Organic Framework

Thermal decomposition of an iron-based MOF was conducted under controlled gas environments to understand the resulting porous carbon structure. Different phases and crystallite sizes of iron oxide are produced based on the specific gas species. In particular, air results in iron(III) oxide, and D₂O and CO₂ results in the mixed valent iron (II,III) oxide. Performing the carbonization under non-oxidative or reducing conditions (N₂, He, H₂) results in the formation of a mixture of both iron (II,III) oxide and iron (III) oxide. Based on in situ and air free handling experiments, it was observed that this is partially due to the formation of zero-valent iron metal that is rapidly oxidized when exposed to air. Neutron pair distribution function analysis provided insight into the effect of the gas environment on the local structure of the porous carbon, indicating a noticeable change in local order between the D₂O and the N₂ calcined samples.