Strong electron correlations in cobalt valence tautomers

We have examined cobalt based valence tautomer molecules such as Co(SQ)$_2$(phen) using density functional theory (DFT) and variational configuration interaction (VCI) approaches based upon a model Hamiltonian. Our DFT results extend earlier work by finding a reduced total energy gap (order 0.6 eV) between high temperature and low temperature states when we fully relax the coordinates (relative to experimental ones). Futhermore we demonstrate that the charge transfer picture based upon formal valence arguments succeeds qualitatively while failing quantitatively due to strong covalency between the Co 3$d$ orbitals and ligand $p$ orbitals. With the VCI approach, we argue that the high temperature, high spin phase is strongly mixed valent, with about 30 % admixture of Co(III) into the predominantly Co(II) ground state. We confirm this mixed valence through a fit to the XANES spectra. Moreover, the strong electron correlations of the mixed valent phase provide an energy lowering of about 0.2-0.3 eV of the high temperature phase relative to the low temperature one. Finally, we use the domain model to account for the extraordinarily large entropy and enthalpy values associated with the transition.Comment: 10 pages, 4 figures, submitted to J. Chem. Phy

How the First Stars Regulated Star Formation. II. Enrichment by Nearby Supernovae

Metals from Population III (Pop III) supernovae led to the formation of less massive Pop II stars in the early universe, altering the course of evolution of primeval galaxies and cosmological reionization. There are a variety of scenarios in which heavy elements from the first supernovae were taken up into second-generation stars, but cosmological simulations only model them on the largest scales. We present small-scale, high-resolution simulations of the chemical enrichment of a primordial halo by a nearby supernova after partial evaporation by the progenitor star. We find that ejecta from the explosion crash into and mix violently with ablative flows driven off the halo by the star, creating dense, enriched clumps capable of collapsing into Pop II stars. Metals may mix less efficiently with the partially exposed core of the halo, so it might form either Pop III or Pop II stars. Both Pop II and III stars may thus form after the collision if the ejecta do not strip all the gas from the halo. The partial evaporation of the halo prior to the explosion is crucial to its later enrichment by the supernova.Comment: Accepted to Ap

Graviton Emission in the Bulk from a Higher-Dimensional Schwarzschild Black Hole

We consider the evaporation of (4+n)-dimensional non-rotating black holes into gravitons. We calculate the energy emission rate for gravitons in the bulk obtaining analytical solutions of the master equation satisfied by all three types (S,V,T) of gravitational perturbations. Our results, valid in the low-energy regime, show a vector radiation dominance for every value of n, while the relative magnitude of the energy emission rate of the subdominant scalar and tensor radiation depends on n. The low-energy emission rate in the bulk for gravitons is well below that for a scalar field, due to the absence of the dominant l=0,1 modes from the gravitational spectrum. Higher partial waves though may modify this behaviour at higher energies. The calculated low-energy emission rate, for all types of degrees of freedom decreases with n, although the full energy emission rate, integrated over all frequencies, is expected to increase with n, as in the previously studied case of a bulk scalar field.Comment: 17 pages, 2 figures, minor corrections, accepted by Phys. Lett.

Optimizing the rheological properties of silica nano-modified bentonite mud using overlaid contour plot and estimation of maximum or upper shear stress limit.

An optimization based statistical (response surface) approach was used to evaluate the rheological properties of bentonite mud treated with silica nanoparticles. The overlaid contour plot established the feasible region for the various factor settings from multiple regression equations. The steepest method was used to further determine the optimal factor settings for minimum rheological properties and this was established at 6.3 wt.% bentonite content and 0.94 wt.% silica nanoparticles. The rheological properties of the bentonite mud containing and without silica nanoparticles was evaluated using a Hyperbolic (new) model and related with other oil industry based models: Herschel Bulkley, Sisko, Casson. The hyperbolic rheological model estimated the rheological behaviour of the nano-modified mud satisfactorily while also predicting a shear stress limit for the nano-modified mud. The maximum shear stress limit values for 6.3, 13 and 15 wt.% mud were 14.59, 61.74 and 107.4 Pa respectively. Upper shear stress values obtained from a 1.5 wt.% silica nanoparticle modified 6.3, 13 and 15 wt.% bentonite mud were 22.27, 72.62 and 171.3 Pa respectively, which represents an increment of 34.5 to 37.4% in the upper limit of shear stress. The effect of silica nanoparticles on the upper shear stress limit was quantified using a response surface design

Observations of the post shock break-out emission of SN 2011dh with XMM-Newton

After the occurrence of the type cIIb SN 2011dh in the nearby spiral galaxy M 51 numerous observations were performed with different telescopes in various bands ranging from radio to gamma-rays. We analysed the XMM-Newton and Swift observations taken 3 to 30 days after the SN explosion to study the X-ray spectrum of SN 2011dh. We extracted spectra from the XMM-Newton observations, which took place ~7 and 11 days after the SN. In addition, we created integrated Swift/XRT spectra of 3 to 10 days and 11 to 30 days. The spectra are well fitted with a power-law spectrum absorbed with Galactic foreground absorption. In addition, we find a harder spectral component in the first XMM-Newton spectrum taken at t ~ 7 d. This component is also detected in the first Swift spectrum of t = 3 - 10 d. While the persistent power-law component can be explained as inverse Compton emission from radio synchrotron emitting electrons, the harder component is most likely bremsstrahlung emission from the shocked stellar wind. Therefore, the harder X-ray emission that fades away after t ~ 10 d can be interpreted as emission from the shocked circumstellar wind of SN 2011dh.Comment: Accepted for publication as a Research Note in Astronomy and Astrophysic

Green's function approach to transport through a gate-all-around Si nanowire under impurity scattering

We investigate transport properties of gate-all-around Si nanowires using non-equilibrium Green's function technique. By taking into account of the ionized impurity scattering we calculate Green's functions self-consistently and examine the effects of ionized impurity scattering on electron densities and currents. For nano-scale Si wires, it is found that, due to the impurity scattering, the local density of state profiles loose it's interference oscillations as well as is broaden and shifted. In addition, the impurity scattering gives rise to a different transconductance as functions of temperature and impurity scattering strength when compared with the transconductance without impurity scattering.Comment: 8 pages, 4 figure

2015 Update on Acute Adverse Reactions to Gadolinium based Contrast Agents in Cardiovascular MR. Large Multi-National and Multi-Ethnical Population Experience With 37788 Patients From the EuroCMR Registry

Objectives: Specifically we aim to demonstrate that the results of our earlier safety data hold true in this much larger multi-national and multi-ethnical population. Background: We sought to re-evaluate the frequency, manifestations, and severity of acute adverse reactions associated with administration of several gadolinium- based contrast agents during routine CMR on a European level. Methods: Multi-centre, multi-national, and multi-ethnical registry with consecutive enrolment of patients in 57 European centres. Results: During the current observation 37788 doses of Gadolinium based contrast agent were administered to 37788 patients. The mean dose was 24.7 ml (range 5–80 ml), which is equivalent to 0.123 mmol/kg (range 0.01 - 0.3 mmol/kg). Forty-five acute adverse reactions due to contrast administration occurred (0.12 %). Most reactions were classified as mild (43 of 45) according to the American College of Radiology definition. The most frequent complaints following contrast administration were rashes and hives (15 of 45), followed by nausea (10 of 45) and flushes (10 of 45). The event rate ranged from 0.05 % (linear non-ionic agent gadodiamide) to 0.42 % (linear ionic agent gadobenate dimeglumine). Interestingly, we also found different event rates between the three main indications for CMR ranging from 0.05 % (risk stratification in suspected CAD) to 0.22 % (viability in known CAD). Conclusions: The current data indicate that the results of the earlier safety data hold true in this much larger multi-national and multi-ethnical population. Thus, the “off-label” use of Gadolinium based contrast in cardiovascular MR should be regarded as safe concerning the frequency, manifestation and severity of acute events

Greybody factors in a rotating black-hole background-II : fermions and gauge bosons

We study the emission of fermion and gauge boson degrees of freedom on the brane by a rotating higher-dimensional black hole. Using matching techniques, for the near-horizon and far-field regime solutions, we solve analytically the corresponding field equations of motion. From this, we derive analytical results for the absorption probabilities and Hawking radiation emission rates, in the low-energy and low-rotation case, for both species of fields. We produce plots of these, comparing them to existing exact numerical results with very good agreement. We also study the total absorption cross-section and demonstrate that, as in the non-rotating case, it has a different behaviour for fermions and gauge bosons in the low-energy limit, while it follows a universal behaviour -- reaching a constant, spin-independent, asymptotic value -- in the high-energy regime.Comment: 22 pages, 8 figures, added reference