The relationship between accreditation status and performance in a proficiency test

In the FAPAS proficiency testing scheme, participants are asked to state whether the analytical method used was accredited or not accredited. It is thus possible to compare the stated accreditation status with performance in the scheme. For this purpose, fifty qualifying examples of analyte-test material combination were selected at random from the reports from the year 2006. The accredited/non-accredited subsets of results from each example were subjected to a statistical analysis to determine whether any significant differences between the distributions of results could be detected. Outliers were removed from the datasets before the main statistical tests and considered separately. The inlying data were subjected to non-parametric tests for differences in central tendency and dispersion. A few significant examples were found, but could be reasonably attributed to chance. Among the inliers there were no grounds to reject the overall null hypothesis, that is, that accreditation has no effect on performance. However, the proportion of outliers was about twice as high among the non-accredited group.     

In situ surface characterization of the intermetallic compound PdGa – A highly selective hydrogenation catalyst

The structurally well-defined intermetallic compound PdGa – a highly selective catalyst for the semi-hydrogenation of acetylene – was characterized by Fourier transform infrared spectroscopy (FTIR) in situ X-ray photoelectron spectroscopy and in situ prompt gamma activation analysis. A strong modification of the electronic states in PdGa compared to elemental Pd was revealed as well as the complete isolation of the Pd atoms on the surface of PdGa. In situ investigations proved the high stability of the surface, thus excluding segregation phenomena (common for alloys) or sub-surface chemistry involving C and/or H atoms (known for elemental Pd). By suppressing the sub-surface chemistry, the electronic modification as well as the site isolation lead to the high selectivity and long-term stability of PdGa in the semi-hydrogenation of acetylene.     

Line mixing effects in the ν2 + ν3 band of methane

This study provides the first direct experimental measurements of the off-diagonal relaxation matrix element coefficients for line mixing in air-broadened methane spectra for any vibrational band and the first off diagonal relaxation matrix elements associated with line mixing for pure methane in the ν₂ + ν₃ band of ¹²CH₄. The speed-dependent Voigt profile with line mixing is used with a multispectrum nonlinear least squares curve fitting technique to retrieve the various line parameters from 11 self-broadened and 10 air-broadened spectra simultaneously. The room temperature spectra analyzed in this work are recorded at 0.011 cm⁻¹ resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory, Kitt Peak, Arizona. The off-diagonal relaxation matrix element coefficients of ν₂ + ν₃ transitions between 4410 and 4629 cm⁻¹ are reported for eighteen pairs with upper state J values between 2 and 11. The observed line mixing coefficients for self broadening vary from 0.0019 to 0.0390 cm⁻¹ atm⁻¹ at 296 K. The measured line mixing coefficients for air broadening vary from 0.0005 to 0.0205 cm⁻¹ atm⁻¹ at 296 K.     

Implementation of Conformal Covariance by Diffeomorphism Symmetry

Every locally normal representation of a local chiral conformal quantum theory is covariant with respect to global conformal transformations, if this theory is diffeomorphism covariant in its vacuum representation. The unitary, strongly continuous representation implementing conformal symmetry is constructed; it consists of operators which are inner in a global sense for the representation of the quantum theory. The construction is independent of positivity of energy and applies to all locally normal representations irrespective of their statistical dimensions (index)     

N=82 shell quenching of the classical r-process "waiting-point" nucleus 130Cd

First beta- and gamma-spectroscopic decay studies of the N=82 r-process "waiting-point" nuclide 130Cd have been performed at CERN/ISOLDE using the highest achievable isotopic selectivity. Several nuclear-physics surprises have been discovered. The first one is the unanticipatedly high energy of 2.12 MeV for the [pi g(9/2) multiply sign in circle nu g(7/2)] 1(+) level in 130In, which is fed by the main Gamow-Teller transition. The second surprise is the rather high Q(beta) value of 8.34 MeV, which is in agreement only with recent mass models that include the phenomenon of N=82 shell quenching. Possible implications of these new results on the formation of the A approximately 130 r-process abundance peak are presented.     

Doppler angle and flow velocity mapping by combined Doppler shift and Doppler bandwidth measurements in optical Doppler tomography

Accurate estimation of flow velocity requires measurement of Doppler angle, which is not available in general clinical applications. We describe a novel method of direct Doppler angle and flow velocity mapping that uses a conventional single-beam optical Doppler tomography system. The Doppler angle is estimated by combination of Doppler shift and Doppler bandwidth measurements, and flow velocity is calculated from the Doppler shift and the estimated Doppler angle. In vivo study of lip microvascularization demonstrates that this method is capable of providing both flow speed and flow direction information.     

Isomeric and ground-state decay of 215 Bi

A new high-spin isomer in ²¹⁵Bi, with a half-life of 36.9(6) s, has been identified at the PSB-ISOLDE on-line mass separator using the pulsed-release technique combined with the element selective RILIS source. A decay scheme of Bi was constructed and complemented with the low-spinstructure observed in Bi decay. The population of a cascade on top of the level in ²¹⁵Poprovides evidence for Gamow-Teller -decay of the high-spin ²¹⁵Bi isomer.Received: 3 March 2003, Revised: 10 June 2003, Published online: 9 October 2003PACS: 23.20.Lv transitions and level energies - 27.80.+w - 29.30.Kv X- and -ray spectroscopyV. Fedoseyev: Present address: ISOLDE, CERN-PPE, CH-1211, Geneva 23, Switzerland.M. Górska: Present address: GSI, Darmstadt, D-64220, Germany.M. Huhta: Present address: Nokia, Tampere, Finland.     

2H( 3He, t)2p reaction at 2 GeV

The exclusive ²H( ³He, t)2p reaction has been studied at 2 GeV for energy transfers up to 500 MeV and triton angles up to 3.4^°. The protons were measured in the large acceptance magnetic detector DIOGENE, in coincidence with the forward tritons detected in a dedicated magnetic arm. The energy transfer spectra extend well above the pion threshold. However, in the region of Δ excitation, the yield is less than 10% of the inclusive ²H( ³He, t) cross-section, which indicates the small contribution of the ΔN ↦ NN process. The angular distributions of the two protons in their center of mass have been analysed as a function of energy transfer and triton angle and a Legendre polynomial decomposition has been achieved. These data have been compared to a model based on a coupled-channel approach for describing the NN and NΔ systems. Received: 21 October 2002 / Accepted: 15 November 2002 / Published online: 11 March 2003 RID="a" ID="a"e-mail: ramstein@ipno.in2p3.fr RID="†" ID="†"Deceased. RID="†" ID="†"Deceased. RID="d" ID="d"Present adress: School of Engineering, J?nk?ping University, P.O. Box 1026, S-551 11 J?nk?ping, Sweden. Communicated by M. Gar?on     

Platinum stilbazoles: ring-walking coupled with aryl-halide bond activation

The reaction between tetrakis(triethylphosphine)platinum(0) and 4-[trans-2-(4-bromophenyl)vinyl]pyridine (1) is examined. Initially, the metal center coordinates to the bridging double bond of 1. Complexes 2 and 3 were fully characterized, and their X-ray crystallography structures are presented. Upon heating, either in solution or in the solid state, complex 2 undergoes C-Br oxidative addition to give complex 3. Kinetic studies revealed that this conversion is unimolecular and does not involve dissociation of the metal center from the double bond. Density functional studies show that a plausible mechanism involves the metal center "walking" around the pi-system from the bridging C=C double bond to the C-Br bond.