Tuning thermally treated graphitic carbon nitride for H₂ evolution and CO₂ photoreduction: The effects of material properties and mid-gap states

Graphitic carbon nitride (g-C3N4) is regarded as an attractive photocatalyst for solar fuel production, i.e., H2 evolution and CO2 photoreduction. Yet, its structural, chemical and optoelectronic properties are very much dependent on the synthesis method and are likely to contribute differently whether H2 evolution or CO2 reduction is considered. Little is known about this aspect making it difficult to tailor g-C3N4 structure and chemistry for a specific photoreaction. Herein, we create g-C3N4 of varying chemical, structural and optical features by applying specific thermal treatments and investigating the effects of the materials properties on solar fuel production. The samples were characterized across scales using spectroscopic, analytical and imaging tools, with particular attention given to the analyses of trap states. In the case of H2 evolution, the reaction is controlled by light absorption and charge separation enabled by the presence of trap states created by N vacancies. In the case of CO2 photoreduction, reactant adsorption appears as a dominating factor. The analyses also suggest that the thermal treatment leads to the formation of trap states located close to the valence band of g-C3N4

Scattering off an oscillating target: Basic mechanisms and their impact on cross sections

We investigate classical scattering off a harmonically oscillating target in two spatial dimensions. The shape of the scatterer is assumed to have a boundary which is locally convex at any point and does not support the presence of any periodic orbits in the corresponding dynamics. As a simple example we consider the scattering of a beam of non-interacting particles off a circular hard scatterer. The performed analysis is focused on experimentally accessible quantities, characterizing the system, like the differential cross sections in the outgoing angle and velocity. Despite the absence of periodic orbits and their manifolds in the dynamics, we show that the cross sections acquire rich and multiple structure when the velocity of the particles in the beam becomes of the same order of magnitude as the maximum velocity of the oscillating target. The underlying dynamical pattern is uniquely determined by the phase of the first collision between the beam particles and the scatterer and possesses a universal profile, dictated by the manifolds of the parabolic orbits, which can be understood both qualitatively as well as quantitatively in terms of scattering off a hard wall. We discuss also the inverse problem concerning the possibility to extract properties of the oscillating target from the differential cross sections.Comment: 18 page

Ordering of the three-dimensional Heisenberg spin glass in magnetic fields

Spin and chirality orderings of the three-dimensional Heisenberg spin glass are studied under magnetic fields in light of the recently developed spin-chirality decoupling-recoupling scenario. It is found by Monte Carlo simulations that the chiral-glass transition and the chiral-glass ordered state, which are essentially of the same character as their zero-field counterparts, occur under magnetic fields. Implication to experimental phase diagram is discussed.Comment: 5 pages, 3 figure

MOBSTER – III. HD 62658: a magnetic Bp star in an eclipsing binary with a non-magnetic ‘identical twin’

HD 62658 (B9p V) is a little-studied chemically peculiar star. Light curves obtained by the Kilodegree Extremely Little Telescope (KELT) and Transiting Exoplanet Survey Satellite (TESS) show clear eclipses with a period of about 4.75 d, as well as out-of-eclipse brightness modulation with the same 4.75 d period, consistent with synchronized rotational modulation of surface chemical spots. High-resolution ESPaDOnS circular spectropolarimetry shows a clear Zeeman signature in the line profile of the primary; there is no indication of a magnetic field in the secondary. PHOEBE modelling of the light curve and radial velocities indicates that the two components have almost identical masses of about 3 M_⊙. The primary’s longitudinal magnetic field〈B_z〉 varies between about +100 and −250 G, suggesting a surface magnetic dipole strength B_d = 850 G. Bayesian analysis of the Stokes V profiles indicates B_d = 650 G for the primary and B_d < 110 G for the secondary. The primary’s line profiles are highly variable, consistent with the hypothesis that the out-of-eclipse brightness modulation is a consequence of rotational modulation of that star’s chemical spots. We also detect a residual signal in the light curve after removal of the orbital and rotational modulations, which might be pulsational in origin; this could be consistent with the weak line profile variability of the secondary. This system represents an excellent opportunity to examine the consequences of magnetic fields for stellar structure via comparison of two stars that are essentially identical with the exception that one is magnetic. The existence of such a system furthermore suggests that purely environmental explanations for the origin of fossil magnetic fields are incomplete

Mott Transition of MnO under Pressure: Comparison of Correlated Band Theories

The electronic structure, magnetic moment, and volume collapse of MnO under pressure are obtained from four different correlated band theory methods; local density approximation + Hubbard U (LDA+U), pseudopotential self-interaction correction (pseudo-SIC), the hybrid functional (combined local exchange plus Hartree-Fock exchange), and the local spin density SIC (SIC-LSD) method. Each method treats correlation among the five Mn 3d orbitals (per spin), including their hybridization with three O $2p$ orbitals in the valence bands and their changes with pressure. The focus is on comparison of the methods for rocksalt MnO (neglecting the observed transition to the NiAs structure in the 90-100 GPa range). Each method predicts a first-order volume collapse, but with variation in the predicted volume and critical pressure. Accompanying the volume collapse is a moment collapse, which for all methods is from high-spin to low-spin (5/2 to 1/2), not to nonmagnetic as the simplest scenario would have. The specific manner in which the transition occurs varies considerably among the methods: pseudo-SIC and SIC-LSD give insulator-to-metal, while LDA+U gives insulator-to-insulator and the hybrid method gives an insulator-to-semimetal transition. Projected densities of states above and below the transition are presented for each of the methods and used to analyze the character of each transition. In some cases the rhombohedral symmetry of the antiferromagnetically ordered phase clearly influences the character of the transition.Comment: 14 pages, 9 figures. A 7 institute collaboration, Updated versio

Valency of rare earths in RIn3 and RSn3: Ab initio analysis of electric-field gradients

In RIn3 and RSn3 the rare earth (R) is trivalent, except for Eu and Yb, which are divalent. This was experimentally determined in 1977 by perturbed angular correlation measurements of the electric-field gradient on a 111Cd impurity. At that time, the data were interpreted using a point charge model, which is now known to be unphysical and unreliable. This makes the valency determination potentially questionable. We revisit these data, and analyze them using ab initio calculations of the electric-field gradient. From these calculations, the physical mechanism that is responsible for the influence of the valency on the electric-field gradient is derived. A generally applicable scheme to interpret electric-field gradients is used, which in a transparent way correlates the size of the field gradient with chemical properties of the system.Comment: 10 page

Enhanced Transmission of Light and Particle Waves through Subwavelength Nanoapertures by Far-Field Interference

Subwavelength aperture arrays in thin metal films can enable enhanced transmission of light and matter (atom) waves. The phenomenon relies on resonant excitation and interference of the plasmon or matter waves on the metal surface. We show a new mechanism that could provide a great resonant and nonresonant transmission enhancement of the light or de Broglie particle waves passed through the apertures not by the surface waves, but by the constructive interference of diffracted waves (beams generated by the apertures) at the detector placed in the far-field zone. In contrast to other models, the mechanism depends neither on the nature (light or matter) of the beams (continuous waves or pulses) nor on material and shape of the multiple-beam source (arrays of 1-D and 2-D subwavelength apertures, fibers, dipoles or atoms). The Wood anomalies in transmission spectra of gratings, a long standing problem in optics, follow naturally from the interference properties of our model. The new point is the prediction of the Wood anomaly in a classical Young-type two-source system. The new mechanism could be interpreted as a non-quantum analog of the superradiance emission of a subwavelength ensemble of atoms (the light power and energy scales as the number of light-sources squared, regardless of periodicity) predicted by the well-known Dicke quantum model.Comment: Revised version of MS presented at the Nanoelectronic Devices for Defense and Security (NANO-DDS) Conference, 18-21 June, 2007, Washington, US

Topological phase transitions between chiral and helical spin textures in a lattice with spin-orbit coupling and a magnetic field

We consider the combined effects of large spin-orbit couplings and a perpendicular magnetic field in a 2D honeycomb fermionic lattice. This system provides an elegant setup to generate versatile spin textures propagating along the edge of a sample. The spin-orbit coupling is shown to induce topological phase transitions between a helical quantum spin Hall phase and a chiral spin-imbalanced quantum Hall state. Besides, we find that the spin orientation of a single topological edge state can be tuned by a Rashba spin-orbit coupling, opening an interesting route towards quantum spin manipulation. We discuss the possible realization of our results using cold atoms trapped in optical lattices, where large synthetic magnetic fields and spin-orbit couplings can be engineered and finely tuned. In particular, this system would lead to the observation of a time-reversal-symmetry-broken quantum spin Hall phase.Comment: 8 pages, 3 figures, Accepted in Europhys. Lett. (Dec 2011

Global climate models violate scaling of the observed atmospheric variability

We test the scaling performance of seven leading global climate models by using detrended fluctuation analysis. We analyse temperature records of six representative sites around the globe simulated by the models, for two different scenarios: (i) with greenhouse gas forcing only and (ii) with greenhouse gas plus aerosol forcing. We find that the simulated records for both scenarios fail to reproduce the universal scaling behavior of the observed records, and display wide performance differences. The deviations from the scaling behavior are more pronounced in the first scenario, where also the trends are clearly overestimated.Comment: Accepted for publishing in Physical Review Letter

Monte Carlo Studies of the Ordering of the Three-Dimensional Isotropic Heisenberg Spin Glass in Magnetic Fields

Spin and chirality orderings of the three-dimensional Heisenberg spin glass under magnetic fields are studied by large-scale equilibrium Monte Carlo simulations. It is found that the chiral-glass transition and the chiral-glass ordered state, which are essentially of the same character as their zero-field counterparts, occur under magnetic fields. The chiral-glass ordered state exhibits a one-step-like peculiar replica-symmetry breaking in the chiral sector, while it does not accompany the spin-glass order perpendicular to the applied field. Critical perperties of the chiral-glass transition are different from those of the standard Ising spin glass. Magnetic phase diagram of the model is constructed, which reveals that the chiral-glass state is quite robust against magnetic fields. The chiral-glass transition line has a character of the Gabay-Toulouse line of the mean-field model, yet its physical origin being entirely different. These numerical results are discussed in light of the recently developed spin-chirality decoupling-recoupling scenario. Implication to experimental phase diagram is also discussed.Comment: 23 pages, 23 figure