Non-equilibrium structural phase transitions of the vortex lattice in MgB2

We have studied non-equilibrium phase transitions in the vortex lattice in superconducting MgB2, where metastable states are observed in connection with an intrinsically continuous rotation transition. Using small-angle neutron scattering and a stop-motion technique, we investigated the manner in which the metastable vortex lattice returns to the equilibrium state under the influence of an ac magnetic field. This shows a qualitative difference between the supercooled case which undergoes a discontinuous transition, and the superheated case where the transition to the equilibrium state is continuous. In both cases the transition may be described by an an activated process, with an activation barrier that increases as the metastable state is suppressed, as previously reported for the supercooled vortex lattice [E. R. Louden et al., Phys. Rev. B 99, 060502(R) (2019)]. Separate preparations of superheated metastable vortex lattices with different domain populations showed an identical transition towards the equilibrium state. This provides further evidence that the vortex lattice metastability, and the kinetics associated with the transition to the equilibrium state, is governed by nucleation and growth of domains and the associated domain boundaries.Comment: 27 pages, 10 figures. arXiv admin note: text overlap with arXiv:1812.0597

Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions

Three [Me2NN]Cu(h2 -L2) complexes (Me2NN ¼ HC[C(Me)NAr]2; L2 ¼ PhNO (2), ArF 2N2 (3), PhCH]CH2 (4); Ar ¼ 2,6-Me2-C6H3; ArF ¼ 3,5-(CF3)2-C6H3) have been studied by Cu K-edge X-ray absorption spectroscopy, as well as single- and multi-reference computational methods (DFT, TD-DFT, CASSCF, MRCI, and OVB). The study was extended to a range of both known and theoretical compounds bearing 2p-element donors as a means of deriving a consistent view of how the pre-edge transition energy responds in systems with significant ground state covalency. The ground state electronic structures of many of the compounds under investigation were found to be strongly influenced by correlation effects, resulting in ground state descriptions with majority contributions from a configuration comprised of a Cu(II) metal center anti-ferromagentically coupled to radical anion O2, PhNO, and ArF 2N2 ligands. In contrast, the styrene complex 4, which displays a Cu K pre-edge transition despite its formal d10 electron configuration, exhibits what can best be described as a Cu(I):(styrene)0 ground state with strong pbackbonding. The Cu K pre-edge features for these complexes increase in energy from 1 to 4, a trend that was tracked to the percent Cu(II)-character in the ground state. The unexpected shift to higher preedge transition energies with decreasing charge on copper (QCu) contributed to an assignment of the pre-edge features for these species as arising from metal-to-ligand charge transfer instead of the traditional Cu1s / Cu3d designation

Magnetic field control of cycloidal domains and electric polarization in multiferroic BiFeO3_3

The magnetic field induced rearrangement of the cycloidal spin structure in ferroelectric mono-domain single crystals of the room-temperature multiferroic BiFeO$_3$ is studied using small-angle neutron scattering (SANS). The cycloid propagation vectors are observed to rotate when magnetic fields applied perpendicular to the rhombohedral (polar) axis exceed a pinning threshold value of $\sim$5\,T. In light of these experimental results, a phenomenological model is proposed that captures the rearrangement of the cycloidal domains, and we revisit the microscopic origin of the magnetoelectric effect. A new coupling between the magnetic anisotropy and the polarization is proposed that explains the recently discovered magnetoelectric polarization to the rhombohedral axis

Structural Transition Kinetics and Activated Behavior in the Superconducting Vortex Lattice

Using small-angle neutron scattering, we investigated the behavior of a metastable vortex lattice state in MgB2 as it is driven towards equilibrium by an AC magnetic field. This shows an activated behavior, where the AC field amplitude and cycle count are equivalent to, respectively, an effective "temperature" and "time". The activation barrier increases as the metastable state is suppressed, corresponding to an aging of the vortex lattice. Furthermore, we find a cross-over from a partial to a complete suppression of metastable domains depending on the AC field amplitude, which may empirically be described by a single free parameter. This represents a novel kind of collective vortex behavior, most likely governed by the nucleation and growth of equilibrium vortex lattice domains.Comment: 5 pages plus 3 pages of supplemental materia

The dehydration, rehydration and tectonic setting of greenstone belts in a portion of the northern Kaapvaal Craton, South Africa

High-grade gneiss terranes and low-grade granite-greenstone terranes are well known in several Archaean domains. The geological relationship between these different crustal regions, however, is still controversial. One school of thought favors fundamental genetic differences between high-grade and low-grade terranes while others argue for a depth-controlled crustal evolution. The detailed examination of well-exposed Archaean terranes at different metamorphic grades, therefore, is not only an important source of information about the crustal levels exposed, but also is critical to the understanding of the possible tectonic and metamorphic evolution of greenstone belts with time. Three South African greenstone belts are compared

Structure–Spectroscopy Correlations for Intermediate Q of Soluble Methane Monooxygenase: Insights from QM/MM Calculations

The determination of the diiron core intermediate structures involved in the catalytic cycle of soluble methane monooxygenase (sMMO), the enzyme that selectively catalyzes the conversion of methane to methanol, has been a subject of intense interest within the bioinorganic scientific community. Particularly, the specific geometry and electronic structure of the intermediate that precedes methane binding, known as intermediate Q (or MMOHQ), has been debated for over 30 years. Some reported studies support a bis-μ-oxo-bridged Fe(IV)2O2 closed-core conformation Fe(IV)2O2 core, whereas others favor an open-core geometry, with a longer Fe–Fe distance. The lack of consensus calls for a thorough re-examination and reinterpretation of the spectroscopic data available on the MMOHQ intermediate. Herein, we report extensive simulations based on a hybrid quantum mechanics/molecular mechanics approach (QM/MM) approach that takes into account the complete enzyme to explore possible conformations for intermediates MMOHox and MMOHQ of the sMMOH catalytic cycle. High-level quantum chemical approaches are used to correlate specific structural motifs with geometric parameters for comparison with crystallographic and EXAFS data, as well as with spectroscopic data from Mössbauer spectroscopy, Fe K-edge high-energy resolution X-ray absorption spectroscopy (HERFD XAS), and resonance Raman 16O–18O difference spectroscopy. The results provide strong support for an open-core-type configuration in MMOHQ, with the most likely topology involving mono-oxo-bridged Fe ions and alternate terminal Fe-oxo and Fe-hydroxo groups that interact via intramolecular hydrogen bonding. The implications of an open-core intermediate Q on the reaction mechanism of sMMO are discussed

Topological energy barrier for skyrmion lattice formation in MnSi

We report the direct measurement of the topological skyrmion energy barrier through a hysteresis of the skyrmion lattice in the chiral magnet MnSi. Measurements were made using small-angle neutron scattering with a custom-built resistive coil to allow for high-precision minor hysteresis loops. The experimental data was analyzed using an adapted Preisach model to quantify the energy barrier for skyrmion formation and corroborated by the minimum-energy path analysis based on atomistic spin simulations. We reveal that the skyrmion lattice in MnSi forms from the conical phase progressively in small domains, each of which consisting of hundreds of skyrmions, and with an activation barrier of several eV.Comment: Final accepted versio