DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

On the observation of the fine structure effect in non- relativistic (e, 2e) processes

The spin asymmetry arising in an (e,2e) process using spin- polarized incoming electrons with non-relativistic energies is shown to be dominated by the fine structure effect if a suitable kinematical regime is chosen. Calculations in the distorted wave Born approximation (DWBA) for both the triple differential cross-section and the spin asymmetry are presented for the inner shell ionization of argon. This process would provide an accessible target for existing experimental set-ups.

Emission-line ratios for [N II] in gaseous nebulae and a comparison between theory and observation

R-matrix calculations of electron impact excitation rates among the 2s(2)2p(2) P-3, D-1, S-1, and 2s2p(3) S-5 levels of N II are presented. These results are used in conjunction with other recent calculations of electron impact excitation rates and Einstein A-coefficients for N II to derive the emission-line ratio: ratio diagrams and where (R-1, R-2) (R-1, R-3), where R-1 = I(5756.2 Angstrom)/I(6549.9 + 6585.2 Angstrom), R-2 = I(2143.5 Angstrom)/I(6549.9 + 6585.2 Angstrom), and R-3 = I(2139.7 Angstrom)/I(6549.9 + 658.2 Angstrom), for a range of electron temperatures (T-e = 5000-20,000 K) and electron densities (N-e = 10(2)-10(7) cm(-3)) appropriate to gaseous nebulae. These diagrams should, in principle, allow the simultaneous determination of T-e and N-e from measurements of the [N II] lines in a spectrum. Plasma parameters deduced for a sample of gaseous nebulae, using observational data obtained from ground-based telescopes plus the International Ultraviolet Explorer and Hubble Space Telescope satellites, are found to show generally excellent internal consistency and to be in good agreement with the values of T-e and N-e estimated from other line ratios. These results provide observational support for the accuracy of the theoretical ratios and hence the atomic data adopted in their derivation. Theoretical ratios are also presented for the infrared line pair R-4 = I(122 mum)/I(205 mum), and the usefulness of R-4 as an electron density diagnostic is briefly discussed.

Aggression after traumatic brain injury: Analysing socially desirable responses and the nature of aggressive traits.

Primary objective: To compare patients with traumatic brain injury (TBI) with controls on sub-types of aggression and explore the role of social desirability.
Design: Quasi-experimental, matched-participants design.
Methods and procedures: Sixty-nine participants were included in the study. The sample comprised a TBI group (n = 24), a spinal cord injury (SCI) group (n = 21) and an uninjured (UI) group of matched healthy volunteers (n = 24). Participants were given self-report measures of aggression, social desirability and impulsivity. Sixty-one independent ‘other-raters’ were nominated, who rated participant pre-morbid and post-morbid aggression.
Main outcomes and results: Using standardized norms, 25–39% of participants with TBI were classified as high average–very high on anger and 35–38% as high average–very high on verbal aggression. Other-raters rated participants with TBI as significantly higher on verbal aggression than SCI and UI participants. There were no differences between the groups on physical aggression. The TBI group also had higher levels of impulsivity than SCI and UI groups. Social desirability was a highly significant predictor of self-reported aggression for the entire sample.
Conclusions: Impulsive verbal aggression and anger are the principal aggressive traits after brain injury. Physical aggression may present in extreme cases after TBI, but appears less prominent overall in this population. Social desirability, previously overlooked in research examining TBI aggression, emerged as an influential variable that should be considered in future TBI research.

Experimental observation of dissociative electron attachment to S2O and S2O2 with a new spectrometer for unstable molecules

A new spectrometer, electron radical interaction chamber, has been developed to study dissociative electron attachment to unstable molecules such as free radicals. It includes a trochoidal electron monochromator and a time-of-flight mass spectrometer. Radicals are generated with a microwave discharge at 2.45 GHz. Preliminary data are presented for radicals formed when a mixture of helium and sulphur dioxide was passed through the microwave discharge. Several new resonances are observed with the discharge on. Resonances at 0 eV (S-), 0.8, 1.2, 3.0 eV (SO-) and 3.7 eV (SO- and S2O-) are assigned to the radical S2O2 and a resonance at 1.6 eV (S-) is assigned to S2O. No new resonances have been assigned to SO, which was also generated in the microwave discharge.

Direct observation of strong coupling in a dense plasma

We present differential x-ray scattering cross sections for a radiatively heated plasma showing overall consistency, in both form and absolute value, with theoretical simulations. In particular, the evolution of the plasma from a strongly coupled high density phase to a lower density weakly coupled phase is quite clearly shown in both experiment and simulation. The success of this experiment shows that x-ray scattering has the potential to become an extremely useful diagnostic technique for dense plasma physics.

Nature of quantum measurement for quantities not represented by Hermitian operators

In the case of a simple quantum system, we investigate the possibility of defining meaningful probabilities for a quantity that cannot be represented by a Hermitian operator. We find that the consistent-histories approach, recently applied to the case of quantum traversal time [N. Yamada, Phys. Rev. Lett. 83, 3350 (1999)], does not provide a suitable criterion and we dispute Yamada's claim of finding a simple solution to the tunneling-time problem. Rather, we define the probabilities for certain types of generally nonorthogonal decomposition of the system's quantum state. These relate to the interaction between the system and its environment, can be observed in a generalized von Neumann measurement, and are consistent with a particular class of positive-operator-valued measures.

Self-cooling of a micro-mirror by radiation pressure

Cooling of mechanical resonators is currently a popular topic in many fields of physics including ultra-high precision measurements, detection of gravitational waves and the study of the transition between classical and quantum behaviour of a mechanical system. Here we report the observation of self-cooling of a micromirror by radiation pressure inside a high-finesse optical cavity. In essence, changes in intensity in a detuned cavity, as caused by the thermal vibration of the mirror, provide the mechanism for entropy flow from the mirror's oscillatory motion to the low-entropy cavity field. The crucial coupling between radiation and mechanical motion was made possible by producing free-standing micromirrors of low mass (m approximately 400 ng), high reflectance (more than 99.6%) and high mechanical quality (Q approximately 10,000). We observe cooling of the mechanical oscillator by a factor of more than 30; that is, from room temperature to below 10 K. In addition to purely photothermal effects we identify radiation pressure as a relevant mechanism responsible for the cooling. In contrast with earlier experiments, our technique does not need any active feedback. We expect that improvements of our method will permit cooling ratios beyond 1,000 and will thus possibly enable cooling all the way down to the quantum mechanical ground state of the micromirror.

Information used in detecting upcoming collisions.

In four experiments we examined the nature of the information used in judging whether events would or would not give rise to a collision in the near future. Observers were tested in situations depicting approaches between two objects (lateral approaches) and approaches between an object and the point of observation (head-on approaches), with objects moving according to constant deceleration or sinusoidal deceleration patterns. Judgments were found to be based, to a large extent, on the (in)sufficiency of current deceleration to avoid upcoming collision, as specified optically by tau-dot (tau over dot). However, the information specified, by tau (tau), that is the current (first-order) time remaining until contact, was also found to play a significant role. We deduce that judgment of upcoming collision is based on the detection Of T and its evolution over time, suggesting that observers are sensitive to Deltatau rather than to tau over dot itself.

On the nature of the circumstellar medium of the remarkable Type Ia/IIn supernova SN 2002ic

We present results from the first high-resolution, high signal-to-noise ratio spectrum of SN 2002ic. The resolved Ha line has a P Cygni-type profile, clearly demonstrating the presence of a dense, slow-moving (~100 km s-1) outflow. We have additionally found a huge near-infrared excess, hitherto unseen in Type Ia supernovae. We argue that this is due to an infrared light-echo arising from the pre-existing dusty circumstellar medium. We deduce a circumstellar medium mass probably exceeding 0.3 Msolar produced by a mass-loss rate greater than several times 10-4 Msolar yr-1. For the progenitor, we favour a single-degenerate system where the companion is a post-asymptotic giant branch star. As a by-product of our optical data, we are able to provide a firm identification of the host galaxy of SN 2002ic.