Hope for Bohemian ecologists – comments on “A possible role of social activity to explain differences in publication output among ecologists?” by Tomáš Grim, Oikos 2008

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CO2 Conversion in Nonuniform Discharges: Disentangling Dissociation and Recombination Mechanisms

Motivated by environmental applications such as synthetic fuel synthesis, plasma-driven conversion shows promise for efficient and scalable gas conversion of CO2 to CO. Both discharge contraction and turbulent transport have a significant impact on the plasma processing conditions, but are, nevertheless, poorly understood. This work combines experiments and modeling to investigate how these aspects influence the CO production and destruction mechanisms in the vortex-stabilized CO2 microwave plasma reactor. For this, a two-dimensional axisymmetric tubular chemical kinetics model of the reactor is developed, with careful consideration of the nonuniform nature of the plasma and the vortex-induced radial turbulent transport. Energy efficiency and conversion of the dissociation process show a good agreement with the numerical results over a broad pressure range from 80 to 600 mbar. The occurrence of an energy efficiency peak between 100 and 200 mbar is associated with a discharge mode transition. The net CO production rate is inhibited at low pressure by the plasma temperature, whereas recombination of CO to CO2 dominates at high pressure. Turbulence-induced cooling and dilution of plasma products limit the extent of the latter. The maxima in energy efficiency observed experimentally around 40% are related to limits imposed by production and recombination processes. Based on these insights, feasible approaches for optimization of the plasma dissociation process are discussed.</p

Orbital and spin physics in LiNiO2 and NaNiO2

We derive a spin-orbital Hamiltonian for a triangular lattice of e_g orbital degenerate (Ni^{3+}) transition metal ions interacting via 90 degree superexchange involving (O^{2-}) anions, taking into account the on-site Coulomb interactions on both the anions and the transition metal ions. The derived interactions in the spin-orbital model are strongly frustrated, with the strongest orbital interactions selecting different orbitals for pairs of Ni ions along the three different lattice directions. In the orbital ordered phase, favoured in mean field theory, the spin-orbital interaction can play an important role by breaking the U(1) symmetry generated by the much stronger orbital interaction and restoring the threefold symmetry of the lattice. As a result the effective magnetic exchange is non-uniform and includes both ferromagnetic and antiferromagnetic spin interactions. Since ferromagnetic interactions still dominate, this offers yet insufficient explanation for the absence of magnetic order and the low-temperature behaviour of the magnetic susceptibility of stoichiometric LiNiO_2. The scenario proposed to explain the observed difference in the physical properties of LiNiO_2 and NaNiO_2 includes small covalency of Ni-O-Li-O-Ni bonds inducing weaker interplane superexchange in LiNiO_2, insufficient to stabilize orbital long-range order in the presence of stronger intraplane competition between superexchange and Jahn-Teller coupling.Comment: 33 pages, 12 postscript figures, uses iopams.sty . This article features in New Journal of Physics as part of a Focus Issue on Orbital Physics - all contributions may be freely accessed at (http://stacks.iop.org/1367-2630/6/i=1/a=E05). The published version of this article may be found at http://stacks.iop.org/1367-2630/7/12

Insight into contraction dynamics of microwave plasmas for CO2 conversion from plasma chemistry modelling

This work addresses plasma chemistry in the core of a vortex-stabilized microwave discharge for CO2 conversion numerically, focusing on the pressure-dependent contraction dynamics of this plasma. A zero-dimensional model is presented for experimental conditions in a pressure range between 60 and 300 mbar and a temperature range between 3000 and 6500 K. Monte Carlo Flux simulations, which describe electron kinetics, are self-consistently coupled to the plasma chemistry model. The simulation results show that an increase in pressure is accompanied by a transition in neutral composition in the plasma core: from a significant amount of CO2 and O2 at low pressures to a O/CO/C mixture at high pressures, the composition being determined mostly by thermal equilibrium and by transport processes. The change of temperature and composition with pressure lead to higher ionisation coefficient and more atomic ion composition in the plasma core. These changes result in an increase in ionisation degree in the plasma core from 10-5 to 10-4. These factors are shown to be fundamental to drive contraction in the CO2 microwave discharge.</p

Characterization of the CO2 microwave plasma based on the phenomenon of skin-depth-limited contraction

The subatmospheric CO2 microwave plasma is known to contract to a narrow filament with rising pressure as result of a mode transition. This changing state of contraction is investigated in relation to its dielectric properties, in order to directly relate the discharge parameters to the discharge radius. The electron density and gas temperature are measured, respectively, by 168 GHz microwave interferometry and Doppler broadening of the 777 nm oxygen emission lines. The plasma is operated in steady state with 1400 W at 2.45 GHz, between 100 mbar and 400 mbar. Electron density values in the central region range from 1018 to 1020 m−3 between the discharge modes, while the gas temperature increases from 3000 K to 6500 K, in good agreement with previously reported values. Based on the dielectric properties of the discharge in relation to the plasma radius, it is found that the discharge column constitutes a radius of a single skin depth. Implications of these insights on the conditions of previously reported CO2 dissociation experiments are discussed.</p

Numerical model for the determination of the reduced electric field in a CO2 microwave plasma derived by the principle of impedance matching

Three dimensional electromagnetic modelling of a free-standing CO2 microwave plasma has been performed, by describing the plasma as a dielectric medium. The relative permittivity and conductivity of the medium are parametrised. The waveguide geometry from experiment, including the tuner, is put into the model, knowing that this corresponds to maximum power transfer of the microwave generator to the plasma under plasma impedance matching conditions. Two CO2 plasma discharge regimes, differing mainly in pressure, input power and temperature, have been studied. The model\u27s validity has been checked through study of materials of known conductivity. From measurements of the neutral gas temperature and the plasma electron density profile, the reduced electric field is determined. From the parametrisation of the dielectric properties, a range for the effective electron-neutral collision frequency for momentum transfer is estimated. The results for the reduced electric field and the range of the electron neutral collision frequency obtained, are consistent as verified by simulations using BOLSIG+. In addition, from this comparison it is possible to narrow down the range of the collision frequencies, and to estimate the electron temperature. The reduced electric field lies between 80 and 180 Td for the relatively low pressure, low input power, the so-called \u27diffuse\u27 regime. For the relatively high pressure, high input power (\u27contracted\u27) regime it lies between 10 and 60 Td. The normalised collision frequency lies between 1.6 and 2.3 for the diffuse regime, while for the contracted regime it lies between 2 and 3. The electron temperature ranges from 2 to 3 eV for the diffuse regime, and from 0.5 to 1 eV for the contracted regime. Related content: 10.1088/1361-6595/ab1ca1</p

Homogeneous Gold Catalysis through Relativistic Effects: Addition of Water to Propyne

In the catalytic addition of water to propyne the Au(III) catalyst is not stable under non-relativistic conditions and dissociates into a Au(I) compound and Cl2. This implies that one link in the chain of events in the catalytic cycle is broken and relativity may well be seen as the reason why Au(III) compounds are effective catalysts.Comment: 12 pages, 3 figures, 1 tabl

Mean-field Study of Charge, Spin, and Orbital Orderings in Triangular-lattice Compounds ANiO2 (A=Na, Li, Ag)

We present our theoretical results on the ground states in layered triangular-lattice compounds ANiO2 (A=Na, Li, Ag). To describe the interplay between charge, spin, orbital, and lattice degrees of freedom in these materials, we study a doubly-degenerate Hubbard model with electron-phonon couplings by the Hartree-Fock approximation combined with the adiabatic approximation. In a weakly-correlated region, we find a metallic state accompanied by \sqroot3x\sqroot3 charge ordering. On the other hand, we obtain an insulating phase with spin-ferro and orbital-ferro ordering in a wide range from intermediate to strong correlation. These phases share many characteristics with the low-temperature states of AgNiO2 and NaNiO2, respectively. The charge-ordered metallic phase is stabilized by a compromise between Coulomb repulsions and effective attractive interactions originating from the breathing-type electronphonon coupling as well as the Hund's-rule coupling. The spin-orbital-ordered insulating phase is stabilized by the cooperative effect of electron correlations and the Jahn-Teller coupling, while the Hund's-rule coupling also plays a role in the competition with other orbital-ordered phases. The results suggest a unified way of understanding a variety of low-temperature phases in ANiO2. We also discuss a keen competition among different spin-orbital-ordered phases in relation to a puzzling behavior observed in LiNiO2

15N in tree rings as a bio-indicator of changing nitrogen cycling in tropical forests: an evaluation at three sites using two sampling methods

Anthropogenic nitrogen deposition is currently causing a more than twofold increase of reactive nitrogen input over large areas in the tropics. Elevated N-15 abundance (delta N-15) in the growth rings of some tropical trees has been hypothesized to reflect an increased leaching of N-15-depleted nitrate from the soil, following anthropogenic nitrogen deposition over the last decades. To find further evidence for altered nitrogen cycling in tropical forests, we measured long-term delta N-15 values in trees from Bolivia, Cameroon, and Thailand. We used two different sampling methods. In the first, wood samples were taken in a conventional way: from the pith to the bark across the stem of 28 large trees (the "radial" method). In the second, delta N-15 values were compared across a fixed diameter (the "fixed-diameter" method). We sampled 400 trees that differed widely in size, but measured delta N-15 in the stem around the same diameter (20 cm dbh) in all trees. As a result, the growth rings formed around this diameter differed in age and allowed a comparison of delta N-15 values over time with an explicit control for potential size-effects on delta N-15 values. We found a significant increase of tree-ring delta N-15 across the stem radius of large trees from Bolivia and Cameroon, but no change in tree-ring delta N-15 values over time was found in any of the study sites when controlling for tree size. This suggests that radial trends of delta N-15 values within trees reflect tree ontogeny (size development). However, for the trees from Cameroon and Thailand, a low statistical power in the fixed-diameter method prevents to conclude this with high certainty. For the trees from Bolivia, statistical power in the fixed-diameter method was high, showing that the temporal trend in tree-ring delta N-15 values in the radial method is primarily caused by tree ontogeny and unlikely by a change in nitrogen cycling. We therefore stress to account for tree size before tree-ring delta N-15 values can be properly interpreted