Transition Probabilities of Co ii Weak Lines to the Ground and Low Metastable Levels.

New branching fraction (BF) measurements based primarily on data from a cross-dispersed echelle spectrometer are reported for 84 lines of Co ii. The BFs for 82 lines are converted to absolute atomic transition probabilities using radiative lifetimes from laser-induced fluorescence (LIF) measurements on 19 upper levels of the lines. A lifetime of 3.3(2) ns for the z5D0 level is used based on LIF measurements for lifetimes of the four other levels in the z5D term. Twelve of the eighty-four lines are weak transitions connecting to the ground and low metastable levels of Co+. Another 46 lines are strong transitions connecting to the ground and low metastable levels of Co+. For these lines, log(gf) values were measured in earlier studies and, with a few exceptions, are confirmed in this study. Such lines, if unblended in stellar spectra, have the potential to yield Co abundance values unaffected by any breakdown of the local thermodynamic equilibrium approximation in stellar photospheres because the ground and low metastable levels of Co+ are the primary population reservoirs of Co in the photospheres of interest. Weak lines, if unblended, are useful in photospheres with high Co abundance, and strong lines are useful in metal-poor photospheres. New hyperfine structure A constants for 28 levels of ionized Co from least-squares fits to Fourier transform spectra line profiles are reported. These laboratory data are applied to re-determine the Co abundance in the metal-poor halo star HD 84937. BFs and transition probabilities for 19 lines are reported for the first time.

IMPROVED Cr II log(gf ) VALUES AND ABUNDANCE DETERMINATIONS IN THE PHOTOSPHERES OF THE SUN AND METAL-POOR STAR HD 84937.

New emission branching fraction (BF) measurements for 183 lines of the second spectrum of chromium (Cr II) and new radiative lifetime measurements from laser-induced fluorescence for 8 levels of Cr+ are reported. The goals of this study are to improve transition probability measurements in Cr II and reconcile solar and stellar Cr abundance values based on Cr I and Cr II lines. Eighteen spectra from three Fourier Transform Spectrometers supplemented with ultraviolet spectra from a high-resolution echelle spectrometer are used in the BF measurements. Radiative lifetimes from this study and earlier publications are used to convert the BFs into absolute transition probabilities. These new laboratory data are applied to determine the Cr abundance log ε in the Sun and metal-poor star HD 84937. The mean result in the Sun is 〈logε (Cr II)〉 = 5.624±0.009 compared to 〈logε(Cr I)〉 = 5.644 ± 0.006 on a scale with the hydrogen abundance log ε(H) = 12 and with the uncertainty representing only line-to-line scatter. A Saha (ionization balance) test on the photosphere of HD 84937 is also performed, yielding 〈logε(Cr II)〉 = 3.417 ± 0.006 and 〈log ε(Cr I, lower level excitation potential E. P. >30 eV)〉 = 3.3743±30.011 for this dwarf star. We find a correlation of Cr with the iron-peak element Ti, suggesting an associated nucleosynthetic production. Four iron-peak elements (Cr along with Ti, V, and Sc) appear to have a similar (or correlated) production history-other iron-peak elements appear not to be associated with Cr.

The impact of recent advances in laboratory astrophysics on our understanding of the cosmos.

An emerging theme in modern astrophysics is the connection between astronomical observations and the underlying physical phenomena that drive our cosmos. Both the mechanisms responsible for the observed astrophysical phenomena and the tools used to probe such phenomena-the radiation and particle spectra we observe-have their roots in atomic, molecular, condensed matter, plasma, nuclear and particle physics. Chemistry is implicitly included in both molecular and condensed matter physics. This connection is the theme of the present report, which provides a broad, though non-exhaustive, overview of progress in our understanding of the cosmos resulting from recent theoretical and experimental advances in what is commonly called laboratory astrophysics. This work, carried out by a diverse community of laboratory astrophysicists, is increasingly important as astrophysics transitions into an era of precise measurement and high fidelity modeling.

Formation, isomerization, and derivatization of Keggin tungstoaluminates.

Trends in the stability of alpha- and beta-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-condensation of Al(III) and W(VI) (2:11 molar ratio) in water gives a pH 7 solution containing beta(1) and beta(2) isomers of [Al(AlOH(2))W(11)O(39)](6)(-) (beta(1)- and beta(2)-1). Partial equilibration of this kinetic product mixture by gentle heating (2 h at 100 degrees C) or, alternatively, co-condensation of Al(III) and W(VI) for 2.5 h at 100 degrees C both give mixtures of beta(2)-, beta(3)-, and alpha-1. Full equilibration, by prolonged heating (25 days at 100 degrees C), gives an isomerically pure solution of alpha-1, thus demonstrating that isomerization occurs in the direction beta(1) --> beta(2) --> beta(3) --> alpha. Furthermore, kinetically controlled conversions of 1 to H(5)[AlW(12)O(40)] (2)-achieved by heating pH 0-0.2 solutions of 1 for 5 days at 100 degrees C-occur with retention of isomeric integrity, such that alpha-1 is converted to alpha-2 (92%; 8% beta), while mixtures of beta(2)- and beta(3)-1 are converted to beta-2 (87%; 13% alpha). These data, when combined with previously reported observations (equilibria between alpha- and beta-2, kinetically controlled hydrolyses of alpha-2 to alpha-[AlW(11)O(39)](9)(-) (alpha-3) and of beta-2 to beta(2)-3, and equilibria between beta(3)- and alpha-3), provide a comprehensive picture regarding the roles of kinetic and thermodynamic control. Finally, a general method for preparation of the isomerically pure derivatives alpha-K(9)(-)(n)()[AlM(n)()(+)W(11)O(39)] (4), M(n)()(+) = Al(III), [V(IV)O](2+), [V(V)O](3+), Mn(II), Mn(III), Mn(IV), Co(II), and Co(III), is provided. The presence of Mn(IV) is confirmed by cyclic voltammetry, pK(a) values of the aquo ligands on 4 are determined by pH titration, and the isomeric structure of these derivatives is established by (27)Al, (51)V, and (183)W NMR and IR spectroscopies and X-ray crystallography.

Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water.

Although many enzymes can readily and selectively use oxygen in water-the most familiar and attractive of all oxidants and solvents, respectively-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical chemistry, which is intrinsically non-selective and difficult to control. In addition, metallo-organic catalysts are inherently susceptible to degradation by oxygen-based radicals, while their transition-metal-ion active sites often react with water to give insoluble, and thus inactive, oxides or hydroxides. Furthermore, pH control is often required to avoid acid or base degradation of organic substrates or products. Unlike metallo-organic catalysts, polyoxometalate anions are oxidatively stable and are reversible oxidants for use with O2 (refs 8,9,10). Here we show how thermodynamically controlled self-assembly of an equilibrated ensemble of polyoxometalates, with the heteropolytungstate anion [AIVVW11O40]6- as its main component, imparts both stability in water and internal pH-management. Designed to operate at near-neutral pH, this system facilitates a two-step O2-based process for the selective delignification of wood (lignocellulose) fibres. By directly monitoring the central Al atom, we show that equilibration reactions typical of polyoxometalate anions keep the pH of the system near 7 during both process steps.