Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn2+, Co2+, Ni2+ and Zn2+) and the 3-amino 4-methyl benzoate ion

Peer reviewed

Coordination networks of Cu2+ ions with 1,3-bis[2-(4-pyridyl)ethyl]benzene : strong structure-directing role of the counter ion (nitrate, acetate and sulphate), leading to clusters, sheets and chains

Date of Acceptance: 16/10/2015

Seawater carbonate chemistry and hydrogen ions and carbonate chemistry in calcifying fluid of coral Astrangia poculata during experiments, 2011

A generalized physicochemical model of the response of marine organisms' calcifying fluids to CO2-induced ocean acidification is proposed. The model is based upon the hypothesis that some marine calcifiers induce calcification by elevating pH, and thus Omega aragonite, of their calcifying fluid by removing protons (H+). The model is explored through two end-member scenarios: one in which a fixed number of H+ is removed from their calcifying fluid, regardless of atmospheric pCO2, and another in which a fixed external-internal proton ratio ([H+]E/[H+]I) is maintained. The model is able to generate the full range of calcification response patterns observed in prior ocean acidification experiments and is consistent with the assertion that organisms' calcification response to ocean acidification is more negative for marine calcifiers that exert weaker control over their calcifying fluid pH. The model is empirically evaluated for the temperate scleractinian coral Astrangia poculata with in situ pH microelectrode measurements of the coral's calcifying fluid under control and acidified conditions. These measurements reveal that (1) the pH of the coral's calcifying fluid is substantially elevated relative to its external seawater under both control and acidified conditions, (2) the coral's [H+]E/[H+]I remains constant under control and acidified conditions, and (3) the coral removes fewer H+ from its calcifying fluid under acidified conditions than under control conditions. Thus, the carbonate system dynamics of A. poculata's calcifying fluid appear to be most consistent with the fixed [H+]E/[H+]I end-member scenario. Similar microelectrode experiments performed on additional taxa are required to assess the model's general applicability.

Freak waves and modulational dynamics in plasmas with negative ions

The nonlinear dynamics of modulated electrostatic wavepackets propagating in negativeion plasmas is investigated from first principles. A nonlinear Schrödinger equation is derived by adopting a multiscale technique. The stability of breather- like (bright envelope soliton) structures, considered as a precursor to freak wave (rogue wave) formation, is investigated and then tested via numerical simulations.<br/>

Radiative rates for E1, E2, M1, and M2 transitions in S-like to F-like tungsten ions (W LIX to W LXVI)

<p>Calculations of energy levels, radiative rates and lifetimes are reported for eight ions of tungsten, i.e. S-like (W LIX) to F-like (W LXVI). A large number of levels have been considered for each ion and extensive configuration interaction has been included among a range of configurations. For the calculations, the general-purpose relativistic atomic structure package (. grasp) has been adopted, and radiative rates (as well as oscillator strengths and line strengths) are listed for all E1, E2, M1, and M2 transitions of the ions. Comparisons have been made with earlier available experimental and theoretical energies, although these are limited to only a few levels for most ions. Therefore for additional accuracy assessments, particularly for energy levels, analogous calculations have been performed with the flexible atomic code (. fac).</p>

Radiative rates for E1, E2, M1, and M2 transitions in Br-like ions with 43≤Z≤50

<p>Energies and lifetimes are reported for the eight Br-like ions with 43≤Z≤50, namely Tc IX, Ru X, Rh XI, Pd XII, Ag XIII, Cd XIV, In XV, and Sn XVI. Results are listed for the lowest 375 levels, which mostly belong to the 4s²4p⁵, 4s²4p⁴4â„“, 4s4p⁶,4s²4p⁴5â„“, 4s²4p³4d², 4s4p⁵4â„“, and 4s4p⁵5â„“ configurations. Extensive configuration interaction among 39 configurations (generating 3990 levels) has been considered and the general-purpose relativistic atomic structure package (grasp) has been adopted for the calculations. Radiative rates are listed for all E1, E2, M1, and M2 transitions involving the lowest 375 levels. Previous experimental and theoretical energies are available for only a few levels of three, namely Ru X, Rh XI and Pd XII. Differences with the measured energies are up to 4% but the present results are an improvement (by up to 0.3 Ryd) in comparison to other recently reported theoretical data. Similarly for radiative rates and lifetimes, prior results are limited to those involving only 31 levels of the 4s²4p⁵, 4s²4p⁴4d, and 4s4p⁶ configurations for the last four ions. Moreover, there are generally no discrepancies with our results, although the larger calculations reported here differ by up to two orders of magnitude for a few transitions.</p>

Radiative rates for E1, E2, M1, and M2 transitions in F-like ions with 37≤Z≤53

<p>Calculations of energy levels, radiative rates and lifetimes are reported for 17 F-like ions with 37≤Z≤53. For brevity, results are only presented among the lowest 113 levels of the 2s²2p⁵, 2s2p⁶, 2s²2p⁴3â„“, 2s2p⁵3â„“, and 2p⁶3â„“ configurations, although the calculations have been performed for up to 501 levels in each ion. The general-purpose relativistic atomic structure package (grasp) has been adopted for the calculations, and radiative rates (along with oscillator strengths and line strengths) are listed for all E1, E2, M1, and M2 transitions of the ions. Comparisons are made with earlier available experimental and theoretical energies, although these are limited to only a few levels for most ions. Therefore for additional accuracy assessments, particularly for energy levels, analogous calculations have been performed with the Flexible Atomic Code (fac), for up to 72 259 levels. Limited previous results are available for radiative rates for comparison purposes, and no large discrepancy is observed for any transition and/or ion.</p>

Reactions of atomic and molecular ions with acetone, 1,1,1- trifluoroacetone, and hexafluoroacetone: An investigation of the effects of molecular structure on the dynamics and kinetics of ion-molecule reactions

<p>A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S⁺, Xe⁺, O⁺, Kr⁺, N⁺, Ar⁺ and Ne⁺) and molecular ions (SF _n⁺ (n = 1-5), CF_n⁺ (n = 1-3), CF₂Cl⁺, H₃O⁺, NO⁺, N ₂O⁺, CO₂⁺, CO⁺, and N₂⁺) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF₃. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H₃O⁺, proton transfer. </p>

Spectroscopy and metastability of CO 2 2+ molecular ions

<p>The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO ₂ ²⁺ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340±0.010 eV. The fragmentation of energy selected CO ₂ ²⁺ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from ∼38.7 to ∼41 eV above the ground state of neutral CO ₂ has been observed in the experimental time window of ∼0.1-2.3 μs with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO ⁺+O ⁺ formation in indirect dissociative double photoionization below the threshold for formation of CO ₂ ²⁺. The threshold for CO ⁺+O ⁺ formation is found to be 35.56±0.10 eV or lower, which is more than 2 eV lower than previous measurements.</p>

The influence of photon excitation and proton irradiation on the luminescence properties of yttria stabilized zirconia doped with praseodymium ions

Lanthanide doped zirconia based materials are promising phosphors for lighting applications. Transparent yttria stabilized zirconia fibres, in situ doped with Pr3+ ions, were grown by the laser floating zone method. The single crystalline doped fibres were found to be homogeneous in composition and provide an intense red luminescence at room temperature. The stability of this luminescence due to transitions between the 1D2 → 3H4 multiplets of the Pr3+ ions (intra-4f2 configuration) was studied by photo- and iono-luminescence. The evolution of the red integrated photoluminescence intensity with temperature indicates that the overall luminescence decreases to ca. 40% of the initial intensity at 14 K when heated to room temperature (RT). RT analysis of the iono-luminescence dependence on irradiation fluence reveals a decrease of the intensity (to slightly more than ∼60% of the initial intensity after 25 min of proton irradiation exposure). Nevertheless the luminescence intensity saturates at non-zero values for higher irradiation fluences revealing good potential for the use of this material in radiation environments.