Understanding Complete Oxidation of Methane on Spinel Oxides at Molecular Level

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo₂O₄ consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo₂O₄ exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. In situ studies of complete oxidation of methane on NiCo₂O₄ and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH₃O with a following dehydrogenation to -CH₂O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.

Photospheric magnetic vortex structures

Using direct numerical magneto-hydrodynamic (MHD) simulations, we demonstrate the evidence of two physically different types of vortex motions in the solar photosphere. Baroclinic motions of plasma in non-magnetic granules are the primary source of vorticity in granular regions of the solar photosphere, however, there is a significantly more efficient mechanism of vorticity production in strongly magnetised intergranular lanes. These swirly motions of plasma in intergranular magnetic field concentrations could be responsible for the generation of different types of MHD wave modes, for example, kink, sausage and torsional Alfven waves. These waves could transport a relevant amount of energy from the lower solar atmosphere and contribute to coronal plasma heating.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Vorticity in the solar photosphere

Aims. We use magnetic and non-magnetic 3D numerical simulations of solar granulation and G-band radiative diagnostics from the resulting models to analyse the generation of small-scale vortex motions in the solar photosphere.
Methods. Radiative MHD simulations of magnetoconvection are used to produce photospheric models. Our starting point is a non-magnetic model of solar convection, where we introduce a uniform magnetic field and follow the evolution of the field in the simulated photosphere. We find two different types of photospheric vortices, and provide a link between the vorticity generation and the presence of the intergranular magnetic field. A detailed analysis of the vorticity equation, combined with the G-band radiative diagnostics, allows us to identify the sources and observational signatures of photospheric vorticity in the simulated photosphere.
Results. Two different types of photospheric vorticity, magnetic and non-magnetic, are generated in the domain. Non-magnetic vortices are generated by the baroclinic motions of the plasma in the photosphere, while magnetic vortices are produced by the magnetic tension in the intergranular magnetic flux concentrations. The two types of vortices have different shapes. We find that the vorticity is generated more efficiently in the magnetised model. Simulated G-band images show a direct connection between magnetic vortices and rotary motions of photospheric bright points, and suggest that there may be a connection between the magnetic bright point rotation and small-scale swirl motions observed higher in the atmosphere.

Stellar Surface Magneto-Convection as a Source of Astrophysical Noise. I. Multi-component Parameterisation of Absorption Line Profiles

We outline our techniques to characterise photospheric granulation as an astrophysical noise source. A four component parameterisation of granulation is developed that can be used to reconstruct stellar line asymmetries and radial velocity shifts due to photospheric convective motions. The four components are made up of absorption line profiles calculated for granules, magnetic intergranular lanes, non-magnetic intergranular lanes, and magnetic bright points at disc centre. These components are constructed by averaging Fe I $6302 \mathrm{\AA}$ magnetically sensitive absorption line profiles output from detailed radiative transport calculations of the solar photosphere. Each of the four categories adopted are based on magnetic field and continuum intensity limits determined from examining three-dimensional magnetohydrodynamic simulations with an average magnetic flux of $200 \mathrm{G}$. Using these four component line profiles we accurately reconstruct granulation profiles, produced from modelling 12 x 12 Mm$^2$ areas on the solar surface, to within $\sim \pm$ 20 cm s$^{-1}$ on a $\sim$ 100 m s$^{-1}$ granulation signal. We have also successfully reconstructed granulation profiles from a $50 \mathrm{G}$ simulation using the parameterised line profiles from the $200 \mathrm{G}$ average magnetic field simulation. This test demonstrates applicability of the characterisation to a range of magnetic stellar activity levels.

The impact of accretion disc winds on the optical spectra of cataclysmic variables

Many high-state non-magnetic cataclysmic variables (CVs) exhibit blueshifted absorption or P-Cygni profiles associated with ultraviolet (UV) resonance lines. These features imply the existence of powerful accretion disc winds in CVs. Here, we use our Monte Carlo ionization and radiative transfer code to investigate whether disc wind models that produce realistic UV line profiles are also likely to generate observationally significant recombination line and continuum emission in the optical waveband. We also test whether outflows may be responsible for the single-peaked emission line profiles often seen in high-state CVs and for the weakness of the Balmer absorption edge (relative to simple models of optically thick accretion discs). We find that a standard disc wind model that is successful in reproducing the UV spectra of CVs also leaves a noticeable imprint on the optical spectrum, particularly for systems viewed at high inclination. The strongest optical wind-formed recombination lines are H alpha and He ii lambda 4686. We demonstrate that a higher density outflow model produces all the expected H and He lines and produces a recombination continuum that can fill in the Balmer jump at high inclinations. This model displays reasonable verisimilitude with the optical spectrum of RW Trianguli. No single-peaked emission is seen, although we observe a narrowing of the double-peaked emission lines from the base of the wind. Finally, we show that even denser models can produce a single-peaked H alpha line. On the basis of our results, we suggest that winds can modify, and perhaps even dominate, the line and continuum emission from CVs.

Interplay of Defects, Magnetism, Ripples and Strain in Graphene

We present a comprehensive study based on first-principles calculations about the interplay of four important ingredients on the electronic structure of graphene: defects + magnetism + ripples + strain. So far they have not been taken into account simultaneously in a set of ab initio calculations. Furthermore, we focus on the strain dependence of the properties of carbon monovacancies, with special attention to magnetic spin moments. We demonstrated that such defects show a very rich structural and spin phase-diagram with many spin solutions as function of strain. At zero strain the vacancy shows a spin moment of 1.5 Bohrs that increases up to 2 Bohrs with stretching. Changes are more dramatic under compression: the vacancy becomes non-magnetic under a compression larger than 2%. This transition is linked to the structural modifications associated with the formation of ripples in the graphene layer. Our results suggest that such interplay could have important implications for the design of future spintronics devices based on graphene derivatives, as for example a spin-strain switch based on vacancies.

Strain-Tunable Spin Moment in Ni-Doped Graphene

Graphene, due to its exceptional properties, is a promising material for nanotechnology applications. In this context, the ability to tune the properties of graphene-based materials and devices with the incorporation of defects and impurities can be of extraordinary importance. Here we investigate the effect of uniaxial tensile strain on the electronic and magnetic properties of graphene doped with substitutional Ni impurities (Ni_sub). We have found that, although Ni_sub defects are non-magnetic in the relaxed layer, uniaxial strain induces a spin moment in the system. The spin moment increases with the applied strain up to values of 0.3-0.4 \mu_B per Ni_sub, until a critical strain of ~6.5% is reached. At this point, a sharp transition to a high-spin state (~1.9 \mu_B) is observed. This magnetoelastic effect could be utilized to design strain-tunable spin devices based on Ni-doped graphene.

Screened Hybrid Exact Exchange Correction Scheme for Adsorption Energies on Perovskite Oxides

The bond formation between an oxide surface and oxygen, which is of importance for numerous surface reactions including catalytic reactions, is investigated within the framework of hybrid density functional theory that includes nonlocal Fock exchange. We show that there exists a linear correlation between the adsorption energies of oxygen on LaMO3 (M = Sc–Cu) surfaces obtained using a hybrid functional (e.g., Heyd–Scuseria–Ernzerhof) and those obtained using a semilocal density functional (e.g., Perdew–Burke–Ernzerhof) through the magnetic properties of the bulk phase as determined with a hybrid functional. The energetics of the spin-polarized surfaces follows the same trend as corresponding bulk systems, which can be treated at a much lower computational cost. The difference in adsorption energy due to magnetism is linearly correlated to the magnetization energy of bulk, that is, the energy difference between the spin-polarized and the non-spin-polarized solutions. Hence, one can estimate the correction ...

Stability of 5-aminolevulinic acid in novel non-aqueous gel and patch-type systems intended for topical application.

Aminolevulinic acid (ALA) stability within topical formulations intended for photodynamic therapy (PDT) is poor due to dimerisation to pyrazine-2,5-dipropionic acid (PY). Most strategies to improve stability use low pH vehicles, which can cause cutaneous irritancy. To overcome this problem, a novel approach is investigated that uses a non-aqueous vehicle to retard proton-induced charge separation across the 4-carbonyl group on ALA and lessen nucleophilic attack that leads to condensation dimerisation. Bioadhesive anhydrous vehicles based on methylvinylether-maleic anhydride copolymer patches and poly(ethyleneglycol) or glycerol thickened poly(acrylic acid) gels were formulated. ALA stability fell below pharmaceutically acceptable levels after 6 months, with bioadhesive patches stored at 5°C demonstrating the best stability by maintaining 86.2% of their original loading. Glycerol-based gels maintained 40.2% in similar conditions. However, ALA loss did not correspond to expected increases in PY, indicating the presence of another degradative process that prevented dimerisation. Nuclear magnetic resonance (NMR) analysis was inconclusive in respect of the mechanism observed in the patch system, but showed clearly that an esterification reaction involving ALA and both glycerol and poly(ethyleneglycol) was occurring. This was especially marked in the glycerol gels, where only 2.21% of the total expected PY was detected after 204 days at 5°C. Non-specific esterase hydrolysis demonstrated that ALA was recoverable from the gel systems, further supporting esterified binding within the gel matrices. It is conceivable that skin esterases could duplicate this finding upon topical application of the gel and convert these derivatives back to ALA in situ, provided skin penetration is not affected adversely.

Quantum manifestations of scattering orbits in the scaled spectrum of a non-hydrogenic atom in crossed fields

Evidence for scattering closed orbits for the Rydberg electron of the singly excited helium atom in crossed electric and magnetic fields at constant scaled energy and constant scaled electric field strength has been found through a quantum calculation of the photo-excitation spectrum. A particular 3D scattering orbit in a mixed regular and chaotic region has been investigated and the hydrogenic 3D closed orbits composing it identified. To the best of our knowledge, this letter reports the first quantum calculation of the scaled spectrum of a non- hydrogenic atom in crossed fields.

A variational approach to the relaxation of single domain magnetic particles based on Brown's model

Brown's model for the relaxation of the magnetization of a single domain ferromagnetic particle is considered. This model results in the Fokker-Planck equation of the process. The solution of this equation in the cases of most interest is non- trivial. The probability density of orientations of the magnetization in the Fokker-Planck equation can be expanded in terms of an infinite set of eigenfunctions and their corresponding eigenvalues where these obey a Sturm-Liouville type equation. A variational principle is applied to the solution of this equation in the case of an axially symmetric potential. The first (non-zero) eigenvalue, corresponding to the largest time constant, is considered. From this we obtain two new results. Firstly, an approximate minimising trial function is obtained which allows calculation of a rigorous upper bound. Secondly, a new upper bound formula is derived based on the Euler-Lagrange condition. This leads to very accurate calculation of the eigenvalue but also, interestingly, from this, use of the simplest trial function yields an equivalent result to the correlation time of Coffey et at. and the integral relaxation time of Garanin. (C) 2004 Elsevier B.V. All rights reserved.

Beyond Ehrenfest: correlated non-adiabatic molecular dynamics

A method for introducing correlations between electrons and ions that is computationally affordable is described. The central assumption is that the ionic wavefunctions are narrow, which makes possible a moment expansion for the full density matrix. To make the problem tractable we reduce the remaining many-electron problem to a single-electron problem by performing a trace over all electronic degrees of freedom except one. This introduces both one- and two-electron quantities into the equations of motion. Quantities depending on more than one electron are removed by making a Hartree-Fock approximation. Using the first-moment approximation, we perform a number of tight binding simulations of the effect of an electric current on a mobile atom. The classical contribution to the ionic kinetic energy exhibits cooling and is independent of the bias. The quantum contribution exhibits strong heating, with the heating rate proportional to the bias. However, increased scattering of electrons with increasing ionic kinetic energy is not observed. This effect requires the introduction of the second moment.

Non-linear conductance of disordered quantum wires

The self-consistent electron potential in a current-carrying disordered quantum wire is spatially inhomogeneous due to the formation of resistivity dipoles across scattering centres. In this paper it is argued that these inhomogeneities in the potential result in a suppression of the differential conductance of such a wire at finite applied voltage. A semi-classical argument allows this suppression, quadratic in the voltage, to be related directly to the amount of intrinsic defect scattering in the wire. This result is then tested against numerical calculations.