2,233 research outputs found
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 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 counts/keV/cm/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
counts/keV/cm/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
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