Is There Enhanced Depletion of Gas-Phase Nitrogen in Moderately Reddened Lines of Sight?

We report on the abundance of interstellar neutral nitrogen (NI) for 30 sightlines, using data from the Far Ultraviolet Spectroscopic Explorer (FUSE) and the Hubble Space Telescope (HST). NI column densities are derived by measuring the equivalent widths of several ultraviolet absorption lines and subsequently fitting those to a curve of growth. We find a mean interstellar N/H of 51+/-4 ppm. This is below the mean found by Meyer et al. of 62(+4,-3) ppm (adjusted for a difference in f-values). Our mean N/H is similar, however, to the (f-value adjusted) mean of 51+/-3 ppm found by Knauth et al. for a larger sample of sightlines with larger hydrogen column densities comparable to those in this study. We discuss the question of whether or not nitrogen shows increased gas-phase depletion in lines of sight with column densities log(H_tot) >~ 21, as claimed by Knauth et al. The nitrogen abundance in the line of sight toward HD 152236 is particularly interesting. We derive very small N/H and N/O ratios for this line of sight that may support a previous suggestion that members of the Sco OB1 association formed from an N-deficient region.Comment: Accepted in The Astrophysical Journal, 9/2006 (expected pub. date: 1/2007) 38 pages, 5 figures (4 color

Thermochromic Absorption And Photoluminescence In [pt(ppy)(mu-ph(2)pz)](2)

The temperature effects on the spectral properties and photophysics of a new d(8)-d(8) dinuclear Pt-II chromophore, [Pt(ppy)(mu-Ph(2)pz)](2) (ppy is 2-phenylpyridine and Ph(2)pz is 3,5-diphenylpyrazolate), have been investigated. The thermochromic shifts are tentatively ascribed to intramolecular sigma interactions between the two pseudocofacial d(Z2) orbitals. Substantial emission profile changes occur in the solid state, solution, and doped polymer films

The relation between column densities of interstellar OH and CH molecules

We present a new, close relation between column densities of OH and CH molecules based on 16 translucent sightlines (six of them new) and confirm the theoretical oscillator strengths of the OH A--X transitions at 3078 and 3082 \AA (0.00105, 0.000648) and CH B--X transitions at 3886 and 3890 \AA, (0.00320, 0.00210), respectively. We also report no difference between observed and previously modelled abundances of the OH molecule.Comment: 4 pages, 0 figures, accepted for publication in MNRA

Chemical Analysis of a Diffuse Cloud along a Line of Sight Toward W51: Molecular Fraction and Cosmic-Ray Ionization Rate

Absorption lines from the molecules OH+, H2O+, and H3+ have been observed in a diffuse molecular cloud along a line of sight near W51 IRS2. We present the first chemical analysis that combines the information provided by all three of these species. Together, OH+ and H2O+ are used to determine the molecular hydrogen fraction in the outskirts of the observed cloud, as well as the cosmic-ray ionization rate of atomic hydrogen. H3+ is used to infer the cosmic-ray ionization rate of H2 in the molecular interior of the cloud, which we find to be zeta_2=(4.8+-3.4)x10^-16 per second. Combining the results from all three species we find an efficiency factor---defined as the ratio of the formation rate of OH+ to the cosmic-ray ionization rate of H---of epsilon=0.07+-0.04, much lower than predicted by chemical models. This is an important step in the future use of OH+ and H2O+ on their own as tracers of the cosmic-ray ionization rate.Comment: 21 pages, 1 figure, 4 table

Supermolecular-Chromophore-Sensitized Near-Infrared-to-Visible Photon Upconversion

Selective near-IR (NIR) excitation (780 nm) of the conjugated supermolecule ruthenium(II) [15-(4?-ethynyl-(2,2?;6?,2??-terpyridinyl))-bis[(5,5?,-10,20-di(2?,6?-bis(3,3-dimethylbutoxy)phenyl)porphinato)zinc(II)]ethyne][4?-pyrrolidin-1-yl-2,2?;6?,2??-terpyridine] bis(hexafluorophosphate) (Pyr1RuPZn2) in solutions containing N,N-bis(ethylpropyl)perylene-3,4,9,10-tetracarboxylicdiimide (PDI) or tetracene gives rise to a substantial anti-Stokes energy gain (PDI, 0.70 eV; tetracene, 0.86 eV). Experimental data clearly demonstrate that this upconverted fluorescence signal is produced via Pyr1RuPZn2-sensitized triplet?triplet annihilation (TTA) photochemistry. The TTA process was confirmed by the quadratic dependence of the integrated 1PDI* emission centered at 541 nm derived from 780 nm laser excitation. The T1?Tn excited state absorption decay of Pyr1RuPZn2, monitored at 900 nm as a function of PDI concentration, revealed Stern?Volmer and bimolecular quenching constants of 10?048 M?1 and 5.9 ? 108 M?1 s?1, respectively, for the PDI triplet sensitization process. The T1?Tn PDI extinction coefficient at 560 nm (εT = 6.6 ? 104 M?1 cm?1) was determined through the triplet energy transfer method utilizing anthracene as the donor chromophore. 3PDI* transient triplet absorption dynamics observed as a function of 485 nm incident nanosecond pump laser fluence demonstrate a bimolecular 3PDI*?3PDI* TTA rate constant (kTT = 1.0 ± 0.2 ? 109 M?1 s?1). The maximum quantum yield of the supermolecule-sensitized PDI upconverted emission (ΦUC = 0.0075 ± 0.0002) was determined relative to [Os(phen)3][PF6]2 at an incident laser power of 22 mW at 780 nm. This study successfully demonstrates NIR-to-visible photon upconversion and achieves a new record anti-Stokes shift of 0.86 eV for sensitized TTA, using the supermolecular Pyr1RuPZn2sensitizer. The stability of the Pyr1RuPZn2/PDI chromophore combination is readily apparent as continuous irradiation at 780 nm produces 541 nm centered fluorescence with no significant decrease in intensity measured over time domains exceeding several hours. The molecular components of these NIR-to-vis upconverting compositions illustrate that substantial anti-Stokes energy gains via a TTA process can be effortlessly realized

On the Ortho:Para Ratio of H3+ in Diffuse Molecular Clouds

The excitation temperature T_01 derived from the relative intensities of the J = 0 (para) and J = 1 (ortho) rotational levels of H2 has been assumed to be an accurate measure of the kinetic temperature in interstellar environments. In diffuse molecular clouds, the average value of T_01 is ~70 K. However, the excitation temperature T(H3+) derived from the (J,K) = (1,1) (para) and (1,0) (ortho) rotational levels of H3+ has been observed to be ~30 K in the same types of environments. In this work, we present observations of H3+ in three additional diffuse cloud sight lines for which H2 measurements are available, showing that in 4 of 5 cases T_01 and T(H3+) are discrepant. We then examine the thermalization mechanisms for the ortho:para ratios of H3+ and H2, concluding that indeed T_01 is an accurate measure of the cloud kinetic temperature, while the ortho:para ratio of H3+ need not be thermal. By constructing a steady-state chemical model taking into account the nuclear-spindependence of reactions involving H3+, we show that the ortho:para ratio of H3+ in diffuse molecular clouds is likely governed by a competition between dissociative recombination with electrons and thermalization via reactive collisions with H2.Comment: 13 pages, 8 figures, 5 tables, accepted for publication in Ap