Charge Transfer in Partition Theory

The recently proposed Partition Theory (PT) [J.Phys.Chem.A 111, 2229 (2007)] is illustrated on a simple one-dimensional model of a heteronuclear diatomic molecule. It is shown that a sharp definition for the charge of molecular fragments emerges from PT, and that the ensuing population analysis can be used to study how charge redistributes during dissociation and the implications of that redistribution for the dipole moment. Interpreting small differences between the isolated parts' ionization potentials as due to environmental inhomogeneities, we gain insight into how electron localization takes place in H2+ as the molecule dissociates. Furthermore, by studying the preservation of the shapes of the parts as different parameters of the model are varied, we address the issue of transferability of the parts. We find good transferability within the chemically meaningful parameter regime, raising hopes that PT will prove useful in chemical applications.Comment: 12 pages, 16 figure

EF+EX Forest Algebras

We examine languages of unranked forests definable using the temporal operators EF and EX. We characterize the languages definable in this logic, and various fragments thereof, using the syntactic forest algebras introduced by Bojanczyk and Walukiewicz. Our algebraic characterizations yield efficient algorithms for deciding when a given language of forests is definable in this logic. The proofs are based on understanding the wreath product closures of a few small algebras, for which we introduce a general ideal theory for forest algebras. This combines ideas from the work of Bojanczyk and Walukiewicz for the analogous logics on binary trees and from early work of Stiffler on wreath product of finite semigroups

Diffuse radio emission in the merging cluster MACS J0717.5+3745: the discovery of the most powerful radio halo

Hierarchical models of structure formation predict that galaxy clusters grow via mergers of smaller clusters and galaxy groups, as well as through continuous accretion of gas. MACS J0717.5+3745 is an X-ray luminous and complex merging cluster, located at a redshift of 0.55. Here we present Giant Metrewave Radio Telescope (GMRT) radio observations at 610 MHz of this cluster. The main aim of the observations is to search for diffuse radio emission within the galaxy cluster MACS J0717.5+3745 related to the ongoing merger. These GMRT observations are complemented by Very Large Array (VLA) archival observations at 1.4, 4.9 and 8.5 GHz. We have discovered a radio halo in the cluster MACS J0717.5+3745 with a size of about 1.2 Mpc. The radio power P_1.4 GHz is 5 x 10^25 W/Hz, which makes it the most powerful radio halo known till date. A 700 kpc radio structure, which we classify as a radio relic, is located in between the merging substructures of the system. The location of this relic roughly coincides with regions of the intra-cluster medium (ICM) that have a significant enhancement in temperature as shown by Chandra. The major axis of the relic is also roughly perpendicular to the merger axis. This shows that the relic might be the result of a merger-related shock wave, where particles are accelerated via the diffuse shock acceleration (DSA) mechanism. Alternatively, the relic might trace an accretion shock of a large-scale galaxy filament to the south-west. The global spectral index of radio emission within the cluster is found to be -1.24 +/-0.05 between 4.9 GHz and 610 MHz. We derive a value of 5.8 microGauss for the equipartition magnetic field strength at the location of the radio halo. [abridged].Comment: 8 pages, 9 figures, accepted for publication in A&A on August 3, 200

Potential, core-level and d band shifts at transition metal surfaces

We have extended the validity of the correlation between the surface 3d-core-level shift (SCLS) and the surface d band shift (SDBS) to the entire 4d transition metal series and to the neighboring elements Sr and Ag via accurate first-principles calculations. We find that the correlation is quasilinear and robust with respect to the differencies both between initial and final-state calculations of the SCLS's and two distinct measures of the SDBS's. We show that despite the complex spatial dependence of the surface potential shift (SPS) and the location of the 3d and 4d orbitals in different regions of space, the correlation exists because the sampling of the SPS by the 3d and 4d orbitals remains similar. We show further that the sign change of the SCLS's across the transition series does indeed arise from the d band-narrowing mechanism previously proposed. However, while in the heavier transition metals the predicted increase of d electrons in the surface layer relative to the bulk arises primarily from transfers from s and p states to d states within the surface layer, in the lighter transition metals the predicted decrease of surface d electrons arises primarily from flow out into the vacuum.Comment: RevTex, 22 pages, 5 figures in uufiles form, to appear in Phys.Rev.

Constraints On Porosity And Mass Loss In O-Star Winds From The Modeling Of X-Ray Emission Line Profile Shapes

We fit X-ray emission line profiles in high resolution XMM-Newton and Chandra grating spectra of the early O supergiant zeta Pup with models that include the effects of porosity in the stellar wind. We explore the effects of porosity due to both spherical and flattened clumps. We find that porosity models with flattened clumps oriented parallel to the photosphere provide poor fits to observed line shapes. However, porosity models with isotropic clumps can provide acceptable fits to observed line shapes, but only if the porosity effect is moderate. We quantify the degeneracy between porosity effects from isotropic clumps and the mass-loss rate inferred from the X-ray line shapes, and we show that only modest increases in the mass-loss rate (less than or similar to 40%) are allowed if moderate porosity effects (h(infinity) less than or similar to R-*) are assumed to be important. Large porosity lengths, and thus strong porosity effects, are ruled out regardless of assumptions about clump shape. Thus, X-ray mass-loss rate estimates are relatively insensitive to both optically thin and optically thick clumping. This supports the use of X-ray spectroscopy as a mass-loss rate calibration for bright, nearby O stars

On The Importance Of The Interclump Medium For Superionization: O VI Formation In The Wind Of Zeta Puppis

We have studied superionization and X-ray line formation in the spectra of zeta Pup using our new stellar atmosphere code (XCMFGEN) that can be used to simultaneously analyze optical, UV, and X-ray observations. Here, we present results on the formation of the O VI lambda lambda 1032, 1038 doublet. Our simulations, supported by simple theoretical calculations, show that clumped wind models that assume void in the interclump space cannot reproduce the observed O vi profiles. However, enough O vi can be produced if the voids are filled by a low-density gas. The recombination of O vi is very efficient in the dense material, but in the tenuous interclump region an observable amount of O vi can be maintained. We also find that different UV resonance lines are sensitive to different density regimes in z Pup: C IV is almost exclusively formed within the densest regions, while the majority of O vi resides between clumps. N v is an intermediate case, with contributions from both the tenuous gas and clumps

Collective Atomic Recoil Laser as a synchronization transition

We consider here a model previously introduced to describe the collective behavior of an ensemble of cold atoms interacting with a coherent electromagnetic field. The atomic motion along the self-generated spatially-periodic force field can be interpreted as the rotation of a phase oscillator. This suggests a relationship with synchronization transitions occurring in globally coupled rotators. In fact, we show that whenever the field dynamics can be adiabatically eliminated, the model reduces to a self-consistent equation for the probability distribution of the atomic "phases". In this limit, there exists a formal equivalence with the Kuramoto model, though with important differences in the self-consistency conditions. Depending on the field-cavity detuning, we show that the onset of synchronized behavior may occur through either a first- or second-order phase transition. Furthermore, we find a secondary threshold, above which a periodic self-pulsing regime sets in, that is immediately followed by the unlocking of the forward-field frequency. At yet higher, but still experimentally meaningful, input intensities, irregular, chaotic oscillations may eventually appear. Finally, we derive a simpler model, involving only five scalar variables, which is able to reproduce the entire phenomenology exhibited by the original model

Boosting clinical performance: The impact of enhanced final year placements.

BACKGROUND: This study follows on from a study that investigated how to develop effective final year medical student assistantship placements, using multidisciplinary clinical teams in planning and delivery. AIMS: This study assessed the effects on objective structured clinical examination (OSCE) performance of the in-course enhanced "super-assistantship" placement introduced to a randomly selected sample of 2013-14 final year medical students at Leeds medical school. METHODS: Quantitative data analysis was used to compare the global grades of OSCE stations between students who undertook this placement against those who did not. RESULTS: There was a small overall improvement in the "super-assistantship" student scores across the whole assessment (effect size = 0.085). "Pre-op Capacity", "Admissions Prescribing" and "Hip Pain" stations had small-medium effect sizes (0.226, 0.215, and 0.214) in favor of the intervention group. Other stations had small effect sizes (0.107-0.191), mostly in favor of the intervention group. CONCLUSIONS: The "super-assistantship" experience characterized by increasing student responsibility on placement can help to improve competence and confidence in clinical decision-making "in a simulated environment". The clinical environment and multidisciplinary team must be ready and supported to provide these opportunities effectively. Further in-course opportunities for increasing final year student responsibility should be developed

Vortices Clustering: The Origin of the Second Peak in the Magnetisation Loops of High Temperature Superconductors

We study vortex clustering in type II Superconductors. We demonstrate that the ``second peak'' observed in magnetisation loops may be a dynamical effect associated with a density driven instability of the vortex system. At the microscopic level the instability shows up as the clustering of individual vortices at (rare) preferential regions of the pinning potential. In the limit of quasi-static ramping the instability is related to a phase transition in the equilibrium vortex system.Comment: 11 pages + 3 figure