Kondo effect in bosonic spin liquids

In a metal, a magnetic impurity is fully screened by the conduction electrons at low temperature. In contrast, impurity moments coupled to spin-1 bulk bosons, such as triplet excitations in paramagnets, are only partially screened, even at the bulk quantum critical point. We argue that this difference is not due to the quantum statistics of the host particles but instead related to the structure of the impurity-host coupling, by demonstrating that frustrated magnets with bosonic spinon excitations can display a bosonic version of the Kondo effect. However, the Bose statistics of the bulk implies distinct behavior, such as a weak-coupling impurity quantum phase transition, and perfect screening for a range of impurity spin values. We discuss implications of our results for the compound Cs2CuCl4, as well as possible extensions to multicomponent bosonic gases.     

Gas-phase and catalytic combustion in heat-recirculating burners

An experimental study of a spiral counterflow “Swiss roll” burner was conducted, with emphasis on the determination of extinction limits and comparison of results with and without bare-metal Pt catalyst. A wide range of Reynolds numbers (Re) were tested using propane–air mixtures. Both lean and rich extinction limits were extended with the catalyst, though rich limits were extended much further. With the catalyst, combustion could be sustained at Re as low as 1.2 with peak temperatures as low as 350 K. A heat transfer parameter characterizing the thermal performance of both gas-phase and catalytic combustion at all Re was identified. At low Re, the “lean” extinction limit was actually rich of stoichiometric, and rich-limit had equivalence ratios exceeded 40 in some cases. No corresponding behavior was observed without the catalyst. Gas-phase combustion, in general, occurred in a “flameless” mode near the burner center. With or without catalyst, for sufficiently robust conditions (high Re, near-stoichiometric) not requiring heat recirculation, a visible flame would propagate out of the center, but this flame could only be re-centered if the catalyst were present. Gas chromatography indicated that at low Re, even in extremely rich mixtures, CO and non-propane hydrocarbons did not form. For higher Re, where both gas-phase and catalytic combustion could occur, catalytic limits were slightly broader but had much lower limit temperatures. At sufficiently high Re, catalytic and gas-phase limits merged. It is concluded that combustion at low Re in heat-recirculating burners greatly benefits from catalytic combustion with the proper choice of mixtures that are different from those preferred for gas-phase combustion. In particular, the importance of providing a reducing environment for the catalyst to enhance O₂ desorption, especially at low Re where heat losses are severe thus peak temperatures are low, is noted.     

Non-perturbative approach to high-index-contrast variations in electromagnetic systems

We present a method that formally calculates exact frequency shifts of an electromagnetic field for arbitrary changes in the refractive index. The possible refractive index changes include both anisotropic changes and boundary shifts. Degenerate eigenmode frequencies pose no problems in the presented method. The approach relies on operator algebra to derive an equation for the frequency shifts, which eventually turn out in a simple and physically sound form. Numerically the equations are well-behaved, easy implementable, and can be solved very fast. Like in perturbation theory a reference system is first considered, which then subsequently is used to solve another related, but different system. For our method precision is only limited by the reference system basis functions and the error induced in frequency is of second order for first-order basis set error. As an example we apply our method to the problem of variations in the air-hole diameter in a photonic crystal fiber.     

Monitoring nanoparticle formation during laser ablation of graphite in an atmospheric-pressure ambient

Excimer laser ablation of highly oriented pyrolytic graphite (HOPG) was performed at atmospheric pressure in an N₂ and in an air ambient. During the ablation, nanoparticles condensed from the material ejecta, and their size distribution was monitored in the gas phase by a Differential Mobility Analyzer (DMA) in combination with a Condensation Particle Counter (CPC). Size distributions obtained at different laser repetition rates revealed that the interaction between subsequent laser pulses and formed particles became significant above 15 Hz. This interaction resulted in laser heating, leading to considerable evaporation and a decrease in the size of the particles. X-ray photoelectron spectroscopy revealed that approximately 8% nitrogen was incorporated into the CN_x particles generated in the N₂ ambient, and that the nitrogen was mostly bonded to sp³-hybridized carbon. Monodisperse particles were also deposited and were analyzed by means of Raman spectroscopy to monitor size-induced effects. PACS 81.07.-b; 61.46.+w; 79.70.+q     

Computerized electroanalysis : Multiple scanning anodic stripping and its application to sea water

the determination of copper, lead, zinc, cadmium and bismuth in standard sea water samples by multiple scanning anodic stripping has been investigated. The influence of plating potential and sample pH has been studied.     

The Dynamic Behaviour and NMR Solution structures of complexes of the type (Bisphosphine)(cycloocta-1,5-diene)iridium(I) and the X-ray crystal structure of (cycloocta-1,5-diene)((−)-norphos)iridium(I) hexafluorophosphate

A square-planar coordination geometry was found for the complex [Ir(cod){(?)-norphos}][PF₆] ( 1b [PF₆]; cod = cylcoocta-1,5-diene and (?)-norphos = [(2R,3R)-8-9-10-trinorborn-5-ene-2,3-diyl]bis(diphenylphosphine)) in the solid state by X-ray diffraction. Crystal data: monoclinic, space group P2₁, a = 10.751 (6), b = 18.669(14), c = 12.037(8) Å, β = 114.82(5)°, Z = 2. A total structural assignment including the configurational and conformational aspects of this and the related compounds [Ir(bishosphine)(cod)]X (bisphosphine = (?)-chiraphos = (2S,3S)-2,3-bis(diphenylphosphino)butane and (?)-norphos, X = Cl, CF₃SO₃, or PF₆) was carried out in solution by one- and two-dimensional NMR spectroscopy. The complexes containing the CF₃SO₃^? and PF₆^? anions are four-coordinate cations with square-planar geometry, whereas the chlorides are five-coordinate neutral compounds showing solvent-dependent dynamic behaviour. In toluene, two diastereoisomers of [IrCl(cod){(?)-norphos}] ( 2b ) exist and interconvert slowly at room temperature. This interchange is fast in CDCl₃ solution, and it is likely to involve Cl dissociation and the formation of the cation [Ir(cod){(?)-norphos}]⁺ as an intermediate.     

Competitive Substitution and Electron Transfer in Reactions between Haloamminegold(III) and Halocyanoaurate(III) Complexes and Thiocyanate

Kinetics for reactions between thiocyanate and trans-Au(CN)(2)Cl(2)(-), trans-Au(CN)(2)Br(2)(-), and trans-Au(NH(3))(2)Cl(2)(+) in an acidic, 1.00 M perchlorate aqueous medium have been studied by use of conventional and diode-array UV/vis spectroscopy and high-pressure and sequential-mixing stopped-flow spectrophotometry. Initial, rapid formation of mixed halide-thiocyanate complexes of gold(III) is followed by slower reduction to Au(CN)(2)(-) and Au(NH(3))(2)(+), respectively. This is an intermolecular process, involving attack on the complex by outer-sphere thiocyanate. Second-order rate constants at 25.0 degrees C for reduction of trans-Au(CN)(2)XSCN(-) are (6.9 +/- 1.1) x 10(4) M(-)(1) s(-)(1) for X = Cl and (3.1 +/- 0.7) x 10(3) M(-)(1) s(-)(1) for X = Br. For reduction of trans-Au(CN)(2)(SCN)(2)(-) the second-order rate constant at 25.0 degrees C is (3.1 +/- 0.1) x 10(2) M(-)(1) s(-)(1) and the activation parameters are DeltaH() = (55 +/- 3) x 10(2) kJ mol(-)(1), DeltaS() = (-17.8 +/- 0.8) J K(-)(1) mol(-)(1), and DeltaV() = (-4.6 +/- 0.5) cm(3) mol(-)(1). The activation volume for substitution of one chloride on trans-Au(NH(3))(2)Cl(2)(+) is (-4.5 +/- 0.5) cm(3) mol(-)(1), and that for reduction of trans-Au(NH(3))(2)(SCN)(2)(+) (4.6 +/- 0.9) cm(3) mol(-)(1). The presence of pi-back-bonding cyanide ligands stabilizes the transition states for both substitution and reductive elimination reactions compared to ammine. In particular, complexes trans-Au(CN)(2)XSCN(-) with an unsymmetric electron distribution along the X-Au-SCN axis are reduced rapidly. The observed entropies and volumes of activation reflect large differences in the transition states for the reductive elimination and substitution processes, respectively, the former being more loosely bound, more sensitive to solvational changes, and probably not involving any large changes in the inner coordination sphere. A transition state with an S-S interaction between attacking and coordinated thiocyanate is suggested for the reduction. The stability constants for formation of the very short-lived complex trans-Au(CN)(2)(SCN)(2)(-) from trans-Au(CN)(2)X(SCN)(-) (X = Cl, Br) by replacement of halide by thiocyanate prior to reduction can be calculated from the redox kinetics data to be K(Cl,2) = (3.8 +/- 0.8) x 10(4) and K(Br,2) = (1.1 +/- 0.4) x 10(2).     

Discovery and validation of urinary exposure markers for different plant foods by untargeted metabolomics

While metabolomics is increasingly used to investigate the food metabolome and identify new markers of food exposure, limited attention has been given to the validation of such markers. The main objectives of the present study were to (1) discover potential food exposure markers (PEMs) for a range of plant foods in a study setting with a mixed dietary background and (2) validate PEMs found in a previous meal study. Three-day weighed dietary records and 24-h urine samples were collected three times during a 6-month parallel intervention study from 107 subjects randomized to two distinct dietary patterns. An untargeted UPLC-qTOF-MS metabolomics analysis was performed on the urine samples, and all features detected underwent strict data analyses, including an iterative paired t test and sensitivity and specificity analyses for foods. A total of 22 unique PEMs were identified that covered 7 out of 40 investigated food groups (strawberry, cabbages, beetroot, walnut, citrus, green beans and chocolate). The PEMs reflected foods with a distinct composition rather than foods eaten more frequently or in larger amounts. We found that 23 % of the PEMs found in a previous meal study were also valid in the present intervention study. The study demonstrates that it is possible to discover and validate PEMs for several foods and food classes in an intervention study with a mixed dietary background, despite the large variability in such a dataset. Final validation of PEMs for intake of foods should be performed by quantitative analysis.

Thermogravimetry study of the effectiveness of different reducing agents during sintering of Cr-prealloyed PM steels

The La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF48) cathode material was used as a protective-conducting coating on an interconnect made of Crofer 22 APU ferritic steel intended for application in intermediate-temperature solid oxide fuel cell (IT-SOFC) stacks. The LSCF48 coating was deposited on the surface of the steel via screen-printing followed by appropriate thermal treatment. The oxidation kinetics of the Crofer 22 APU steel—uncoated and coated with LSCF48—approximately obeys the parabolic rate law in air at 1,073 K under isothermal and cyclic oxidation conditions. The oxidation rate for uncoated steel is higher than that for coated steel. SEM–EDS and XRD investigations showed that the LSCF48 coating interacts with the steel during long-term oxidation in the afore-mentioned thermal conditions, and an intermediate multilayer interfacial zone is formed. This intermediate layer leads to lower area specific resistance in air at 1,073 K in comparison to the Crofer 22 APU steel without surface modification.