Varying spin state composition by the choice of capping ligand in a family of molecular chains: detailed analysis of magnetic properties of chromium(III) horseshoes

We report a detailed physical analysis on a family of isolated, antiferro-magnetically (AF) coupled, chromium(III) finite chains, of general formula (Cr(RCO(2))(2)F)(n) where the chain length n = 6 or 7. Additionally, the chains are capped with a selection of possible terminating ligands, including hfac (= 1,1,1,5,5,5-hexafluoropentane-2,4-dionate(1-)), acac (= pentane-2,4-dionate(1-)) or (F)(3). Measurements by inelastic neutron scattering (INS), magnetometery and electron paramagnetic resonance (EPR) spectroscopy have been used to study how the electronic properties are affected by n and capping ligand type. These comparisons allowed the subtle electronic effects the choice of capping ligand makes for odd member spin 3/2 ground state and even membered spin 0 ground state chains to be investigated. For this investigation full characterisation of physical properties have been performed with spin Hamiltonian parameterisation, including the determination of Heisenberg exchange coupling constants and single ion axial and rhombic anisotropy. We reveal how the quantum spin energy levels of odd or even membered chains can be modified by the type of capping ligand terminating the chain. Choice of capping ligands enables Cr-Cr exchange coupling to be adjusted by 0, 4 or 24%, relative to Cr-Cr exchange coupling within the body of the chain, by the substitution of hfac, acac or (F)(3) capping ligands to the ends of the chain, respectively. The manipulation of quantum spin levels via ligands which play no role in super-exchange, is of general interest to the practise of spin Hamilton modelling, where such second order effects are generally not considered of relevance to magnetic properties.

Effect of pulsatility on the mathematical modeling of rotary blood pumps

In this study, the effect of time derivatives of flow rate and rotational speed was investigated on the mathematical modeling of a rotary blood pump (RBP). The basic model estimates the pressure head of the pump as a dependent variable using measured flow and speed as predictive variables. Performance of the model was evaluated by adding time derivative terms for flow and speed. First, to create a realistic working condition, the Levitronix CentriMag RBP was implanted in a sheep. All parameters from the model were physically measured and digitally acquired over a wide range of conditions, including pulsatile speed. Second, a statistical analysis of the different variables (flow, speed, and their time derivatives) based on multiple regression analysis was performed to determine the significant variables for pressure head estimation. Finally, different mathematical models were used to show the effect of time derivative terms on the performance of the models. In order to evaluate how well the estimated pressure head using different models fits the measured pressure head, root mean square error and correlation coefficient were used. The results indicate that inclusion of time derivatives of flow and speed can improve model accuracy, but only minimally.

(Non)-Dissipative Hydrodynamics on Embedded Surfaces

We construct the theory of dissipative hydrodynamics of uncharged fluids living on embedded space-time surfaces to first order in a derivative expansion in the case of codimension-1 surfaces (including fluid membranes) and the theory of non-dissipative hydrodynamics to second order in a derivative expansion in the case of codimension higher than one under the assumption of no angular momenta in transverse directions to the surface. This construction includes the elastic degrees of freedom, and hence the corresponding transport coefficients, that take into account transverse fluctuations of the geometry where the fluid lives. Requiring the second law of thermodynamics to be satisfied leads us to conclude that in the case of codimension-1 surfaces the stress-energy tensor is characterized by 2 hydrodynamic and 1 elastic independent transport coefficient to first order in the expansion while for codimension higher than one, and for non-dissipative flows, the stress-energy tensor is characterized by 7 hydrodynamic and 3 elastic independent transport coefficients to second order in the expansion. Furthermore, the constraints imposed between the stress-energy tensor, the bending moment and the entropy current of the fluid by these extra non-dissipative contributions are fully captured by equilibrium partition functions. This analysis constrains the Young modulus which can be measured from gravity by elastically perturbing black branes.

What does professionalisation mean? Perceptions of professionalisation in swiss sport federations

Introduction: Organisational changes in sports federations are often associated with a drift from a volunteer driven to an increasingly business-like phenomenon (Shilbury & Ferkins, 2011). This process of transfor-mation is be called as “professionalization”. Accordingly, professionalization seems to be an appropriate strategy for sport organisations in order to meet organizational pressure due to challenges of a more complex and dynamic changing environment adequately. Despite the increasing research interest and the attempts for systematization on the phenomenon of professionalization it still remains unclear what does the term professionalization exactly mean (Dowling et al., 2014). Thus, there is a lack of a consistent concept of professionalization that is needed in order to explore different facets and perspectives of this phenomenon more validly. Against this background following question emerged: What is the suitable concept of professionalization for analyzing the actual ongoing processes of change, adaption or transformation in sport federations? Methods: Dealing with this question, following two-step approach was choosen: (1) In a first step a scholar’s perspective at professionalisation of sport organisations will be displayed in order to explore both the common ground as well as divergences and inconsistencies in previous approaches. Therefore, a literature review is indicated. (2) In a second step, and in contrast to previous studies we will consider a practical point of view by a so called second-order observation of experts to gain valuable insights into current thinking and acting towards professionalization in sport federations. In doing so, a hermeneutical approach is used, which is about understanding the meaning of contexts by grasping the everyday world, and draw insight and meaning from it (Shilbury et al., 2013). Accordance with hermeneutics, the explorative interpretive knowledge of expert interviews was used. The interviews were conducted with a sample of six selected experts, who have both dedicated insider knowledge and the overall view of all Swiss sport federations. Results and discussion: The summaries of literature review could be categorized into two research currents. The one defines professionalization as a structural process towards professional status of occupations. The other defines it in a broader sense as an organisational change towards a business-like approach. Whereas the first perspective there is a broad scientific consensus that second isn’t that clear, however. Explorative analysis of interview data reveals different themes in relation to professionalization of sports federation. First theme deals with a changed philosophy as more strategic alignment towards for-profit, efficiency and quality orientation. Second theme refers to paid work associated with more competence orientation and balanced governance between paid and voluntary work. Third theme deals with acting shift towards more rationalization and efficiency by implementation of innovative management and communication tools. Based on findings of both our review of scholar`s perspective as well insights from experts we will provide – in the sense of synthesis – a more clear understanding of what does professionalization mean that can be useful in terms of further studies. References: Dowling, M., Edwards, J. & Washington, M. (2014). Understanding the concept of professionalisation in sport management research. Sport Management Review, 17 (4), 520–529. Shilbury, D., Ferkins, L. & Smythe, L. (2013). Sport governance encounters: Insights from lived experiences. Sport Management Review, 16,349–363. Shilbury, D., & Ferkins, L. (2011). Professionalisation, sport governance and strategic capability. Managing Leisure, 16, 108–127.

Excitonic Splitting, Delocalization, and Vibronic Quenching in the Benzonitrile Dimer

The excitonic S1/S2 state splitting and the localization/delocalization of the S1 and S2 electronic states are investigated in the benzonitrile dimer (BN)2 and its 13C and d5 isotopomers by mass-resolved two-color resonant two-photon ionization spectroscopy in a supersonic jet, complemented by calculations. The doubly hydrogen-bonded (BN-h5)2 and (BN-d5)2 dimers are C2h symmetric with equivalent BN moieties. Only the S0 → S2 electronic origin is observed, while the S0 → S1 excitonic component is electric-dipole forbidden. A single 12C/13C or 5-fold h5/d5 isotopic substitution reduce the dimer symmetry to Cs, so that the heteroisotopic dimers (BN)2-(h5 – h513C), (BN)2-(h5 – d5), and (BN)2-(h5 – h513C) exhibit both S0 → S1 and S0 → S2 origins. Isotope-dependent contributions Δiso to the excitonic splittings arise from the changes of the BN monomer zero-point vibrational energies; these range from Δiso(12C/13C) = 3.3 cm–1 to Δiso(h5/d5) = 155.6 cm–1. The analysis of the experimental S1/S2 splittings of six different isotopomeric dimers yields the S1/S2 exciton splitting Δexc = 2.1 ± 0.1 cm–1. Since Δiso(h5/d5) ≫ Δexc and Δiso(12C/13C) > Δexc, complete and near-complete exciton localization occurs upon 12C/13C and h5/d5 substitutions, respectively, as diagnosed by the relative S0 → S1 and S0 → S2 origin band intensities. The S1/S2 electronic energy gap of (BN)2 calculated by the spin-component scaled approximate second-order coupled-cluster (SCS-CC2) method is Δelcalc = 10 cm–1. This electronic splitting is reduced by the vibronic quenching factor Γ. The vibronically quenched exciton splitting Δelcalc·Γ = Δvibroncalc = 2.13 cm–1 is in excellent agreement with the observed splitting Δexc = 2.1 cm–1. The excitonic splittings can be converted to semiclassical exciton hopping times; the shortest hopping time is 8 ps for the homodimer (BN-h5)2, the longest is 600 ps for the (BN)2(h5 – d5) heterodimer.

New Algorithms for M-Estimation of Multivariate Scatter and Location

We present new algorithms for M-estimators of multivariate scatter and location and for symmetrized M-estimators of multivariate scatter. The new algorithms are considerably faster than currently used fixed-point and related algorithms. The main idea is to utilize a second order Taylor expansion of the target functional and to devise a partial Newton-Raphson procedure. In connection with symmetrized M-estimators we work with incomplete U-statistics to accelerate our procedures initially.

Grain coarsening in contact metamorphic carbonates: effects of second-phase particles, fluid flow and thermal perturbations

Under contact metamorphic conditions, carbonate rocks in the direct vicinity of the Adamello pluton reflect a temperature-induced grain coarsening. Despite this large-scale trend, a considerable grain size scatter occurs on the outcrop-scale indicating local influence of second-order effects such as thermal perturbations, fluid flow and second-phase particles. Second-phase particles, whose sizes range from nano- to the micron-scale, induce the most pronounced data scatter resulting in grain sizes too small by up to a factor of 10, compared with theoretical grain growth in a pure system. Such values are restricted to relatively impure samples consisting of up to 10 vol.% micron-scale second-phase particles, or to samples containing a large number of nano-scale particles. The obtained data set suggests that the second phases induce a temperature-controlled reduction on calcite grain growth. The mean calcite grain size can therefore be expressed in the form D 1⁄4 C2 eQ*/RT(dp/fp)m*, where C2 is a constant, Q* is an activation energy, T the temperature and m* the exponent of the ratio dp/fp, i.e. of the average size of the second phases divided by their volume fraction. However, more data are needed to obtain reliable values for C2 and Q*. Besides variations in the average grain size, the presence of second-phase particles generates crystal size distribution (CSD) shapes characterized by lognormal distributions, which differ from the Gaussian-type distributions of the pure samples. In contrast, fluid-enhanced grain growth does not change the shape of the CSDs, but due to enhanced transport properties, the average grain sizes increase by a factor of 2 and the variance of the distribution increases. Stable d18O and d13C isotope ratios in fluid-affected zones only deviate slightly from the host rock values, suggesting low fluid/rock ratios. Grain growth modelling indicates that the fluid-induced grain size variations can develop within several ka. As inferred from a combination of thermal and grain growth modelling, dykes with widths of up to 1 m have only a restricted influence on grain size deviations smaller than a factor of 1.1.To summarize, considerable grain size variations of up to one order of magnitude can locally result from second-order effects. Such effects require special attention when comparing experimentally derived grain growth kinetics with field studies.