Branching Fractions and Transition Probabilities for UV Transitions in the Spectrum of Cr ii
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Jacob W. Ward↗
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Oscillator strengths for Fe II transitions at 224.918 and 226.008 nanometers
We report accurate experimental absorption oscillator strengths (f-values) for transitions out of the ground level of Fe II to the Z(sup 4)D(sup 0 sub 7/2) and z(sup 4)F(sup 0 sub 9/2) levels at 224.918 and 226.008 nm (air wavelengths) to be 0.00182(14) and 0.00244(19), respectively. The number in parenthesis is the uncertainty in the last digits. These two lines are important for studying Fe abundances and grain depletions in the interstellar medium. These f-values are determined by combining emission branching fractions with radiative lifetimes. Branching fractions are measured using classical spectroradiometry on an optically thin source. Radiative lifetimes are from the literature.
Bergeson, S. D.↗
Oscillator strengths of the Si II 181 nanometer resonance multiplet
We report Si II experimental log (gf)-values of -2.38(4) for the 180.801 nm line, of -2.18(4) for the 181.693 nm line, and of -3.29(5) for the 181.745 nm line, where the number in parentheses is the uncertainty in the last digit. The overall uncertainties (about 10 percent) include the 1 sigma random uncertainty (about 6 percent) and an estimate of the systematic uncertainty. The oscillator strengths are determined by combining branching fractions and radiative lifetimes. The branching fractions are measured using standard spectroradiometry on an optically thin source; the radiative lifetimes are measured using time-resolved laser-induced fluorescence.
Bergeson, S. D.↗
Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene
This work reports measurements of absolute rate coefficients and Rice-Ramsperger-Kassel-Marcus (RRKM) master equation simulations of the C2H3 + C2H4 reaction. Direct kinetic studies were performed over a temperature range of 300-700 K and pressures of 20 and 133 mbar. Vinyl radicals (H2C=CH) were generated by laser photolysis of vinyl iodide (C2H31) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals through absorption at 423.2 nm. Measurements at 20 mbar are in good agreement with previous determinations at higher temperature. A weighted three-parameter Arrhenius fit to the experimental rate constant at 133 mbar, with the temperature exponent fixed, gives k = (7 +/- 1) x 10(exp -l4) cu cm/molecule/s (T/298 K)(exp 2) exp[-(1430 +/- 70) K/T]. RRKM master equation simulations, based on G3 calculations of stationary points on the C4H7 potential energy surface, were carried out to predict rate coefficients and product branching fractions. The predicted branching to 1-methylallyl product is relatively small under the conditions of the present experiments but increases as the pressure is lowered. Analysis of end products of 248 nm photolysis of vinyl iodide/ethylene mixtures at total pressures between 27 and 933 mbar provides no direct evidence for participation of I -methylallyl.
Ismail, Huzeifa↗
Atomic Oscillator Strengths in the Vacuum Ultraviolet
We have developed techniques to measure branching fractions in the vacuum ultraviolet using diffraction grating spectroscopy and phosphor image plates as detectors. These techniques have been used to measure branching fractions in Fe II that give prominent emission lines in astrophysical objects.
Nave, Gillian↗
Inclusive gamma-ray spectra from psi/3095/ and psi-prime/3684/ decays
Inclusive gamma-ray experiments were carried out in a e(+)e(-) colliding-beam apparatus with NaI(Tl) arrays as detectors. The inclusive gamma-ray spectra, after cosmic-ray background subtraction, are shown as histograms for the decays of the psi(3095) and psi-prime(3684). The psi spectrum has no significant narrow structure, while the psi-prime spectrum shows at least four peaks. Three major radiative decays of the psi-prime(3684) are found, and their respective branching fractions are computed.
Biddick, C. J.↗
Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr
Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.
Haugen, H. K.↗
Laboratory studies of the kinetics of tropospheric and stratospheric atom and radical reactions
Direct measurements of reaction rate constants and branching fractions for elementary reactions necessary in the modeling of the troposphere or stratosphere are provided. Details of reaction mechanisms are elucidated by studying pressure and temperature dependences of reactions, as well as by use of isotopic labels. Measurement techniques are improved for radical species in the laboratory. Progress and results in each area are given.
Golde, Michael F.↗
Radiative lifetimes, branching rations, and absolute transition probabilities in Cr II and Zn II
New absolute atomic transition probability measurements are reported for 12 transitions in Cr II and two transitions in Zn II. These transition probabilities are determined by combining branching ratios measured by classical techniques and radiative lifetimes measured by time-resolved laser-induced fluorescence. The measurements are compared with branching fractions, radiative lifetimes, and transition probabilities in the literature. The 206 nm resonance multiplets in Cr II and Zn II are included in this work. These multiplets are very useful in determining the distribution of the elements in the gas versus grain phases in the interstellar medium.
Bergeson, S. D.↗
Transition probabilities for the 3s2 3p(2P0)-3s3p2(4P) intersystem lines of Si II
Intensity ratios of lines of the spin-changing 'intersystem' multiplet of S II (4P yields 2P0) at 234 nm have been used to determine electron densities and temperatures in a variety of astrophysical environments. However, the accuracy of these diagnostic calculations have been limited by uncertainties associated with the available atomic data. We report the first laboratory measurement, using an ion-trapping technique, of the radiative lifetimes of the three metastable levels of the 3s3p2 4P term of Si II. Our results are 104 +/- 16, 406 +/- 33, and 811 +/- 77 micro-s for lifetimes of the J = 1/2, 5/2, and 3/2 levels, respectively. A-values were derived from our lifetimes by use of measured branching fractions. Our A-values, which differ from calculated values by 30 percent or more, should give better agreement between modeled and observed Si II line ratios.
Calamai, Anthony G.↗
Comparison of new experimental and atrophysical f-values for some Ru II lines, observed in HST spectra of chi Lupi
We report an experimental absolute oscillator strengths for 18 UV lines of Ru II, obtained by combining laser-induced flourescence measurements of radiative lifetimes and branching fractions from line intensities in a calibrated Fourier-transform spectrum Hubble Space Telescope/Goddard High Resolution Spectrograph (HST/GHRS) observations of the spectrum of the sharp-lined B star chi Lupi contain six of these lines, for which 'astrophysical' relative f-values have been determined. The agreement is within 0.10 dex for a Ru abundance of log N(Ru)/N(H) = -7.90, which is 2.3 dex above the solar abundance.
Johansson, Sveneric G.↗
Laboratory Astrophysics Under the Ultraviolet, Visible, and Gravitational Astrophysics Research Program
Space-borne facilities, such as the Hubble Space Telescope, the recent ORFEUS-SPAS II Shuttle mission, and the soon-to-be launched Far Ultraviolet Spectroscopic Explorer, are providing data at ultraviolet wavelengths of unprecedented quality for spectroscopic studies of many astronomical environments. The first step in the analysis of these data involves the derivation of abundances. Obtaining accurate abundances is possible only when the correspondence between line strength and abundance is well known. The conversion of line strength to abundance relies on knowledge of transition probabilities and oscillator strengths, often obtained from mean lives branching fractions. For many ultraviolet transitions, the necessary atomic and molecular data are either relatively imprecise or not available. Our program addresses this need for accurate oscillator strengths; our focus is on transitions that probe the nature and composition of the interstellar medium.
Federman, Steven R.↗
Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K
The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.
Thorn, R. Peyton, Jr.↗
A Spatial Heterodyne Spectrometer for Laboratory Astrophysics; First Interferogram
A Spatial Heterodyne Spectrometer with broad spectral coverage across the VUV - UV region and with a high (> 500,000 ) spectral resolving power is being built for laboratory measurements of spectroscopic data including emission branching fractions, improved level energies, and hyperfine/isotopic parameters.
Lawler, J. E.↗
Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction
Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.
Selby, Talitha M.↗
Carbon Isotopic Fractionation Associated with Cyanobacterial Biomarkers: 2-Methylhopanoids and Methyl-Branched Alkanes
This paper reports the carbon isotopic fractionations associated with the biosynthesis of biomarker lipids in a number of cyanobacteria obtained from culture collections and isolated from the coniform mats of Yellowstone National Park. Additional information is contained in the original extended abstract.
Jahnke, L. L.↗
X-ray variability of Scorpius X-1 during a multiwavelength campaign
Consideration is given to the X-ray variability of Scorpius X-1, which was observed with Ginga on March 9-11, 1989 as part of a multiwavelength campaign. The temporal characteristics observed, including quasi-periodic oscillations, HF noise, and VLF noise, are consistent with previous observations of Sco X-1. Quasi-periodic oscillations are observed on both the normal branch and the lower flaring branch, but not on the upper flaring branch. Limits are placed on the fractional rms variation of quasi-period oscillations on the upper flaring branch of less than or approximately equal to 2 percent of the total intensity. The characteristics of the observed red noise components are found to vary along the flaring branch. The fractional rms variation of VLF noise increases from less than 2 to greater than 6 percent as Sco X-1 moves from the flaring branch-normal branch vertex to the upper end of the flaring branch.
Hertz, P.↗
Tri- and tetraterpenoid hydrocarbons in the Messel oil shale
The high-molecular-weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high-resolution gas chromatography and combined gas chromatography/mass spectrometry. The following compounds are present: perhydrolycopene, together with one or more unsaturated analogs with the same skeleton; a series of 4-methylsteranes in higher abundance than their 4-desmethyl analogs; two series of pentacyclic triterpanes, one series based on the hopane structure, and the other based on the 17 alpha-H hopane structure; and an intact triterpene hop-17(21)-ene. Only two additional triterpanes were detected in minor concentrations - namely, 30-normoretane and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment.
Kimble, B. J.↗