Nonbonding pairs in cyclic thioethers: Electrostatic modelling and ab initio calculations for complexes of 2,5-dihydrothiophene, thietane and thiirane with hydrogen fluoride

Electrostatic potential energies V(ϕ) of a non‐perturbing, protonic charge at fixed distances r from the S atom in three cyclic thioethers were examined as functions of the angles ϕ made by the r‐vector with the C2 axis (thiirane and 2,5‐dihydrothiophene) or the local C2 axis (thietane). The electrostatic PE VHF(ϕ) of HF (HF modelled as an extended electric dipole) was also calculated and the results compared with geometries of the thioether⋯HF complexes calculated at the CCSD(T)‐F12c/cc‐pVTZ‐F12 level. The latter reveal angular deviations θ ∼10‐20° of the S⋯H-F nuclei from collinearity in directions suggesting secondary interactions of F with H atom(s) of the rings. Angles ϕ made by the S⋯H hydrogen bond with the C2 (or local C2) axes in the complexes are systematically larger (∼4‐9°) than indicated by the VHF(ϕ) functions. Minima in the simple V(ϕ) versus ϕ functions occur at values smaller (∼5‐10°) than those in the VHF(ϕ) curves

Microzooplankton regulation of surface ocean POC:PON ratios

The elemental composition of particulate organic matter in the surface ocean significantly affects the efficiency of the ocean's store of carbon. Though the elemental composition of primary producers is an important factor, recent observations from the western North Atlantic Ocean revealed that carbon-to-nitrogen ratios (C:N) of phytoplankton were significantly higher than the relatively homeostatic ratio of the total particulate pool (particulate organic carbon:particulate organic nitrogen; POC:PON). Here we use an idealized ecosystem model to show how interactions between primary and secondary producers maintain the mean composition of surface particulates and the difference between primary producers and bulk material. Idealized physiological models of phytoplankton and microzooplankton, constrained by laboratory data, reveal contrasting autotrophic and heterotrophic responses to nitrogen limitation: under nitrogen limitation, phytoplankton accumulate carbon in carbohydrates and lipids while microzooplankton deplete internal C reserves to fuel respiration. Global ecosystem simulations yield hypothetical global distributions of phytoplankton and microzooplankton C:N ratio predicting elevated phytoplankton C:N ratios in the high-light, low-nutrient regions of the ocean despite a lower, homeostatic POC:PON ratio due to respiration of excess carbon in systems subject to top-down control. The model qualitatively captures and provides a simple interpretation for, a global compilation of surface ocean POC:PON data

An ab initio investigation of alkali-metal non-covalent bonds BLiR and BNaR (R = F, H or CH3) formed with simple Lewis bases B : the relative inductive effects of F, H and CH3

The alkali-metal bonds formed by simple molecules LiR and NaR (R = F, H or CH3) with each of the six Lewis bases B = OC, HCN, H2O, H3N, H2S and H3P were investigated by ab initio calculations at the CCSD(T)/AVTZ and CCSD(T)/awCVTZ levels of theory with the aim of characterising this type of non-covalent interaction. In some complexes, two minima were discovered, especially for those involving the NaR. The higher-energy minimum (referred to as Type I) for a given B was found to have geometry that is isomorphous with that of the corresponding hydrogen-bonded analogue BHF. The lower-energy minimum (when two were present) showed evidence of a significant secondary interaction of R with the main electrophilic region of B (Type II complexes). Energies D_e^"CBS" for dissociation of the complexes into separate components were found to be directly proportional to the intermolecular stretching force constant kσ The value of D_e^"CBS" could be partitioned into a nucleophilicity of B and an electrophilicity of LiR or NaR, with the order ELiH ≳ ELiF = ELiCH3 for the LiR and ENaF > ENaH ≈ ENaCH3 for the NaR. For a given B, the order of the electrophilicities is ELiR > ENaR , which presumably reflects the fact that Li+ is smaller than Na+ and can approach the Lewis base more closely. A SAPT analysis revealed that the complexes BLiR and BNaR have larger electrostatic contributions to De than do the hydrogen- and halogen-bonded counterparts BHCl and BClF

No Evidence Supporting Flare Driven High-Frequency Global Oscillations

The underlying physics that generates the excitations in the global low-frequency, < 5.3 mHz, solar acoustic power spectrum is a well known process that is attributed to solar convection; However, a definitive explanation as to what causes excitations in the high-frequency regime, > 5.3 mHz, has yet to be found. Karoff and Kjeldsen (Astrophys. J. 678, 73-76, 2008) concluded that there is a correlation between solar flares and the global high-frequency solar acoustic waves. We have used the Global Oscillations Network Group (GONG) helioseismic data in an attempt to verify Karoff and Kjeldsen (2008) results as well as compare the post-flare acoustic power spectrum to the pre-flare acoustic power spectrum for 31 solar flares. Among the 31 flares analyzed, we observe that a decrease in acoustic power after the solar flare is just as likely as an increase. Furthermore, while we do observe variations in acoustic power that are most likely associated with the usual p-modes associated with solar convection, these variations do not show any significant temporal association with flares. We find no evidence that consistently supports flare driven high-frequency waves.Comment: 20 pages, 9 figures, Accepted for publication in Solar Physic

High Pressure Thermoelasticity of Body-centered Cubic Tantalum

We have investigated the thermoelasticity of body-centered cubic (bcc) tantalum from first principles by using the linearized augmented plane wave (LAPW) and mixed--basis pseudopotential methods for pressures up to 400 GPa and temperatures up to 10000 K. Electronic excitation contributions to the free energy were included from the band structures, and phonon contributions were included using the particle-in-a-cell (PIC) model. The computed elastic constants agree well with available ultrasonic and diamond anvil cell data at low pressures, and shock data at high pressures. The shear modulus $c_{44}$ and the anisotropy change behavior with increasing pressure around 150 GPa because of an electronic topological transition. We find that the main contribution of temperature to the elastic constants is from the thermal expansivity. The PIC model in conjunction with fast self-consistent techniques is shown to be a tractable approach to studying thermoelasticity.Comment: To be appear in Physical Review

Violation of the Wiedemann-Franz Law in a Large-N Solution of the t-J Model

We show that the Wiedemann-Franz law, which holds for Landau Fermi liquids, breaks down in a large-n treatment of the t-J model. The calculated ratio of the in-plane thermal and electrical conductivities agrees quantitatively with experiments on the normal state of the electron-doped Pr_{2-x}Ce_xCuO_4 (x = 0.15) cuprate superconductor. The violation of the Wiedemann-Franz law in the uniform phase contrasts with other properties of the phase that are Fermi liquid like.Comment: 4 pages, 2 figures. Typos corrected, one added reference, revised discussion of experiment on 214 cuprate material (x = 0.06

Magnetic Fields in the 3C 129 Cluster

We present multi-frequency VLA observations of the two radio galaxies 3C 129 and 3C 129.1 embedded in a luminous X-ray cluster. These radio observations reveal a substantial difference in the Faraday Rotation Measures (RMs) toward 3C 129.1 at the cluster center and 3C 129 at the cluster periphery. After deriving the density profile from available X-ray data, we find that the RM structure of both radio galaxies can be fit by a tangled cluster magnetic field with strength 6 microGauss extending at least 3 core radii (450 kpc) from the cluster center. The magnetic field makes up a small contribution to the total pressure (5%) in the central regions of the cluster. The radio morphology of 3C 129.1 appears disturbed on the southern side, perhaps by the higher pressure environment. In contrast with earlier claims for the presence of a moderately strong cooling flow in the 3C 129 cluster, our analysis of the X-ray data places a limit on the mass deposition rate from any such flow of <1.2 Msun/yr.Comment: in press at MNRA

Low Background Micromegas in CAST

Solar axions could be converted into x-rays inside the strong magnetic field of an axion helioscope, triggering the detection of this elusive particle. Low background x-ray detectors are an essential component for the sensitivity of these searches. We report on the latest developments of the Micromegas detectors for the CERN Axion Solar Telescope (CAST), including technological pathfinder activities for the future International Axion Observatory (IAXO). The use of low background techniques and the application of discrimination algorithms based on the high granularity of the readout have led to background levels below 10$^{-6}$ counts/keV/cm$^2$/s, more than a factor 100 lower than the first generation of Micromegas detectors. The best levels achieved at the Canfranc Underground Laboratory (LSC) are as low as 10$^{-7}$ counts/keV/cm$^2$/s, showing good prospects for the application of this technology in IAXO. The current background model, based on underground and surface measurements, is presented, as well as the strategies to further reduce the background level. Finally, we will describe the R&D paths to achieve sub-keV energy thresholds, which could broaden the physics case of axion helioscopes.Comment: 6 pages, 3 figures, Large TPC Conference 2014, Pari

On slip pulses at a sheared frictional viscoelastic/ non deformable interface

We study the possibility for a semi-infinite block of linear viscoelastic material, in homogeneous frictional contact with a non-deformable one, to slide under shear via a periodic set of ``self-healing pulses'', i.e. a set of drifting slip regions separated by stick ones. We show that, contrary to existing experimental indications, such a mode of frictional sliding is impossible for an interface obeying a simple local Coulomb law of solid friction. We then discuss possible physical improvements of the friction model which might open the possibility of such dynamics, among which slip weakening of the friction coefficient, and stress the interest of developing systematic experimental investigations of this question.Comment: 23 pages, 3 figures. submitted to PR