Analysis of evening and morning transitions in complex terrain: MATERHORN campaign 2013

A field study of thermal circulation over very gentle slope is described for a specific day characterised by weak synoptic conditions. The emphasis was on morning and evening transitions, but measurements cover the entire day; therefore a brief analysis is performed to represent the general thermal circulation pattern. Both transition periods are characterised by complex dynamic behaviours. During evening transition, the upslope flow has got through a stagnation condition characterised by wind velocity U<0:5 m=s. Only when the stagnating air has become negative buoyant, the flow is allowed to pour downslope like a slab. Some features of front formation has been found during the transition development, such as delay time of downslope flow start up along the slope, and the presence of positive turbulent kinetic energy at the onset of the motion. Eventually the observed evening transition has followed a mixed mechanisms, with features from different models. Therefore the Rayleigh number seems not to be a good criterion by which parametrise evening transition itself. Morning transition is characterised by destruction of nocturnal temperature inversion and the onset of upslope flow. Inversion destruction can be described in terms of CBL growth at surface and inversion decent from the top of the layer. KH has found to be a good indicator of inversion breakup, if used as parameter to study the inversion breakup in terms of temperature reversal. After the inversion breakup, buoyancy and mechanical productions supply the flow with the necessary energy to start the upslope wind. More quantitative analysis are provided by the study of stability parameters and turbulent kinetic energy budgets. Gradient Richardson number has been used in this terms, finding that a mixed SBL-CBL behaviour dominates the most of the observed layers. Tke budget has shown high turbulent behaviour during morning transition while the evening transition has developed entirely in laminar condition, apart from short intermittent turbulent events.

Conformational transitions of glycine induced by vibrational excitation of the O-H stretch

Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the v = 1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (v = 1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed.

Enhanced (1)G(4) emission in NaLaF4: Pr3+, Yb3+ and charge transfer in NaLaF4: Ce3+, Yb3+ studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF4: 1%Pr3+, 5%Yb3+ and NaLaF4: 1%Ce3+, 5%Yb3+ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr3+(P-3(0) -> (1)G(4), Yb3+(F-2(7/2) -> F-2(5/2)) energy transfer step takes place, significant Pr3+ (1)G(4) emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr3+ and Yb3+ can be given. In the case of NaLaF4: Ce3+, Yb3+ it is concluded that the observed Yb3+ emission upon Ce3+ 5d excitation is the result of a charge transfer process instead of down-conversion. (C) 2010 Elsevier B.V. All rights reserved.

Risks and Responsibilities? The Individualisation of Youth Transitions and the Ambivalence between Participation and Activation in Europe

This report provides insight on the situation facing young people in contemporary European societies in their transitions to work and citizenship. On the one hand, risks of exclusion have increased, while on the other, responsibilities for coping with such risks have been individualised, a state of affairs reinforced by the trend towards activation labour market policies. Drawing on the findings of a EU-funded study across nine European regions, the report gives evidence of the resulting biographical and policy dilemmas. Furthermore, it explores if and under what conditions the concept of participation may open new ways of reconciling systemic imperatives and individual needs in the social integration of young people.

Hyalotekite, (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2)(Si,B)(2)O28F, a Tectosilicate Related to Scapolite: New Structure Refinement, Phase Transitions and a Short-Range Ordered 3B Superstructure

Hyalotekite, a framework silicate of composition (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2) (Si,B)(2)O28F, is found in relatively high-temperature(greater than or equal to 500 degrees C) Mn skarns at Langban, Sweden, and peralkaline pegmatites at Dara-i-Pioz, Tajikistan. A new paragenesis at Dara-i-Pioz is pegmatite consisting of the Ba borosilicates leucosphenite and tienshanite, as well as caesium kupletskite, aegirine, pyrochlore, microcline and quartz. Hyalotekite has been partially replaced by barylite and danburite. This hyalotekite contains 1.29-1.78 wt.% Y2O3, equivalent to 0.172-0.238 Y pfu or 8-11% Y on the Ca site; its Pb/(Pb+Ba) ratio ranges 0.36-0.44. Electron microprobe F contents of Langban and Dara-i-Pioz hyalotekite range 1.04-1.45 wt.%, consistent with full occupancy of the F site. A new refinement of the structure factor data used in the original structural determination of a Langban hyalotekite resulted in a structural formula, (Pb1.96Ba1.86K0.18)Ca-2(B1.76Be0.24)(Si1.56B0.44)Si8O28F, consistent with chemical data and all cations with positive-definite thermal parameters, although with a slight excess of positive charge (+57.14 as opposed to the ideal +57.00). An unusual feature of the hyalotekite framework is that 4 of 28 oxygens are non-bridging; by merging these 4 oxygens into two, the framework topology of scapolite is obtained. The triclinic symmetry of hyalotekite observed at room temperature is obtained from a hypothetical tetragonal parent structure via a sequence of displacive phase transitions. Some of these transitions are associated with cation ordering, either Pb-Ba ordering in the large cation sites, or B-Be and Si-B ordering on tetrahedral sites. Others are largely displacive but affect the coordination of the large cations (Pb, Ba, K, Ca). High-resolution electron microscopy suggests that the undulatory extinction characteristic of hyalotekite is due to a fine mosaic microstructure. This suggests that at least one of these transitions occurs in nature during cooling, and that it is first order with a large volume change. A diffuse superstructure observed by electron diffraction implies the existence of a further stage of short-range cation ordering which probably involves both (Pb,K)-Ba and (BeSi,BB)-BSi.

Modellieren im Mathematik- und Physikunterricht

Dieses Projekt war eine Fortsetzung der Zusammenarbeit der Lehrpersonen in den Fächern Mathematik und Physik in der 7A Klasse, 11. Schulstufe. Es ging vor allem darum, das „Kasterldenken, zu überwinden“, bzw. den Wissenstransfer zwischen den beiden Fächern zu schaffen. Gründe für die Schwierigkeiten beim Erreichen dieses Zieles dürften in den vergangenen beiden Jahren darin gelegen sein, dass die Projektarbeit in die Leistungsbeurteilung mit einbezogen worden war und dass seitens der Lehrer/innen die Anforderungen an die Schüler/innen viel zu hoch angesetzt waren. Die Begleitung und Betreuung durch Universitätsprofessorin Tina Hascher und zwei Diplomand/innen brachte eine neue Außensicht herein. Der entscheidende Schlüssel zur Veränderung der Situation bestand darin, dass durch die Beistellung der neuesten Literatur und der Beachtung der dort angeführten Rahmenbedingungen der Wissenstransfer bei einem Großteil der Schüler/innen gelang.

Phase Transitions of YbBr2

The crystalline phases of YbBr2 were investigated by powder neutron diffraction between 1.5 K and the melting point at 955 K (682 °C). The low temperature SrI2 phase is observed up to 550 K, the α-PbO2 phase between 260 K and 750 K, the CaCl2 phase between 690 K and 790 K, and the rutile phase from 790 K to the melting point. All observed phase transitions are first order, except for the second order CaCl2 to rutile transition. The transition temperatures and enthalpies were determined by differential scanning calorimetry.

How Cantonal Education Systems in Switzerland Promote Gender-Typical School-to-Work Transitions

The paper asks how cantonal education systems in Switzerland promote gender-typed school-to-work transitions and gender segregation at work. Data from the Swiss TREE youth panel study is used to analyse the impact of cantonal provision of vocational education and training (VET) on gender-typical educational trajectories. The findings show that education systems with higher VET rates have higher allocations of men in gender-(male-) typical occupational careers. The paper concludes that the pronounced and persistent gender segregation on the Swiss labor market is partly due to a prominent VET system, which urges early gender-typed occupational career decisions.

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Comparison of 2.5D and 3D Quantification of Femoral Head Coverage in Normal Control Subjects and Patients with Hip Dysplasia.

Hip dysplasia is characterized by insufficient femoral head coverage (FHC). Quantification of FHC is of importance as the underlying goal of the surgery to treat hip dysplasia is to restore a normal acetabular morphology and thereby to improve FHC. Unlike a pure 2D X-ray radiograph-based measurement method or a pure 3D CT-based measurement method, previously we presented a 2.5D method to quantify FHC from a single anteriorposterior (AP) pelvic radiograph. In this study, we first quantified and compared 3D FHC between a normal control group and a patient group using a CT-based measurement method. Taking the CT-based 3D measurements of FHC as the gold standard, we further quantified the bias, precision and correlation between the 2.5D measurements and the 3D measurements on both the control group and the patient group. Based on digitally reconstructed radiographs (DRRs), we investigated the influence of the pelvic tilt on the 2.5D measurements of FHC. The intraclass correlation coefficients (ICCs) for absolute agreement was used to quantify interobserver reliability and intraobserver reproducibility of the 2.5D measurement technique. The Pearson correlation coefficient, r, was used to determine the strength of the linear association between the 2.5D and the 3D measurements. Student's t-test was used to determine whether the differences between different measurements were statistically significant. Our experimental results demonstrated that both the interobserver reliability and the intraobserver reproducibility of the 2.5D measurement technique were very good (ICCs > 0.8). Regression analysis indicated that the correlation was very strong between the 2.5D and the 3D measurements (r = 0.89, p < 0.001). Student's t-test showed that there were no statistically significant differences between the 2.5D and the 3D measurements of FHC on the patient group (p > 0.05). The results of this study provided convincing evidence demonstrating the validity of the 2.5D measurements of FHC from a single AP pelvic radiograph and proved that it could serve as a surrogate for 3D CT-based measurements. Thus it may be possible to use this method to avoid a CT scan for the purpose of estimating 3D FHC in diagnosis and post-operative treatment evaluation of patients with hip dysplasia.