Effect of spin-orbit excitation on chemical reactivity - Laser transient absorption spectroscopy of Br(2P1/2, 2P3/2) + IBr reactive dynamics
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Haugen, H. K.↗
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Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers
Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.
Scott, G. W.↗
Measurements of kinetic processes in a self-sustained discharge XeF laser
Measurements are presented for processes occurring in XeF self-sustained discharges including fluorescence, gain, and absorption at different wavelengths as a function of F2, Xe, and He partial pressures. Time-correlated oscillograms are given for the laser discharge current, metastable XeF small-signal gain at 351.1 nm, transient absorptions at 333.6 and 363.8 nm, metastable-XeF B-state sidelight emission at about 350 nm, metastable-F emission at 634.8 nm, and metastable-F emission at 731.1 nm. It is found that He atoms are necessary for the production of metastable-XeF in its lower vibrational levels and that radiative processes and He quenching are the primary mechanisms for metastable-XeF decay. For small-signal gains of as low as about 8%/cm, the transient absorption at the laser wavelength may be as large as about 1-2%/cm.
Gower, M. C.↗
Kinetics of the Reaction C2H + O2 from 193 to 350 K Using Laser Flash Kinetic Infrared Absorption Spectroscopy
Rate coefficients for the reaction C2H + O2 are measured from 193 to 350 K by using transient absorption spectroscopy with an infrared color center laser. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a temperature variable flow cell and a tunable color center laser probes the transient removal Of C2H ((bar-X(sup 2))Sigma(+))(0,0,0)) in absorption. The rate coefficient has a slight negative temperature dependence over the range 193-350 K which can be expressed as k(O2) = (1.5 +/- 0.3) x 10(exp -11) exp((230 +/- 36)/T) Cu cm/(Molecule.s). The lack of a pressure dependence under our experimental conditions strongly suggests that the HCCOO* complex is short lived with respect to encountering a collision and rapidly dissociates to products without competition from collisional stabilization to HCCOO or collisionally induced dissociation to reactants.
Opansky, Brian J.↗
Femtosecond optical absorption studies of nonequilibrium electronic processes in high T(c) superconductors
The results are reported of femtosecond optical transient absorption experiments performed on the superconducting compounds YBa2Cu3O(7-x) (x about 0) and Bi2Sr2Ca2Cu3O(10+delta) (delta about 0) and nonsuperconducting YBa2Cu3O(6+y) (y less than 0.4) for sample temperatures ranging from about 7 K to room temperature. Nonequilibrium heating was found to occur on a subpicosecond time scale. A distinct, dramatic increase in the relaxation time was observed for the superconducting samples as the sample temperature was lowered below the critical temperatures of the respective films. Accompanying the increase in relaxation time was an increase in the peak fractional transmissivity change. No such changes were observed for the nonsuperconducting YBCO sample.
Chwalek, J. M.↗
Photochemistry of bromoacetylene - Formation of HBr and quenching of excited Br/4 2P 0 1/2/
The photolysis of bromacetylene is examined by means of vacuum ultraviolet flash photolysis-kinetic spectroscopy, with attention given to the production of Br atoms in the 2P 0 3/2 and 2P 0 1/2 states, the production of HBr, and UV absorption attributable to the ethynyl radical. Although Br(2P 0 1/2) and Br(2P 0 3/2) were both directly observed at the shortest delay time after the flash, strongly indicating the presence of the ethynyl radical, transient absorption by C2H was not detected in the range 125 to 180 nm. Quenching rate constants for the decay of the 2P 0 1/2 state of Br, which is observed to form concurrently with the ground state, are derived for quenching by He, CH2Br, CF4, and D2 from the pseudo-first-order decay rates. HBr was observed as a secondary photolysis product, and a model of its formation by the exothermic reaction of ground-state atoms with C2HBR, coupled with the secondary production of Br atoms, is found to agree well with the experiment.
Laufer, A. H.↗
Eta Carinae: An Evolving View of the Central Binary, Its Interacting Winds and Its Foreground Ejecta
FUV spectra of η Car, recorded across two decades with HST/STIS, document multiple changes in resonant lines caused by dissipating extinction in our line of sight. The FUV flux has increased nearly tenfold, which has led to increased ionization of the multiple shells within the Homunculus and photodestruction of H 2 . Comparison of observed resonant line profiles with CMFGEN model profiles allows separation of wind–wind collision and shell absorptions from the primary wind P Cygni profiles. The dissipating occulter preferentially obscured the central binary and interacting winds relative to the very extended primary wind. We are now able to monitor changes in the colliding winds with orbital phase. High-velocity transient absorptions occurred across the most recent periastron passage, indicating acceleration of the primary wind by the secondary wind, which leads to a downstream, high-velocity bow shock that is newly generated every orbital period. There is no evidence of changes in the properties of the binary winds.
Massive stars↗
Studying Absorption Line Feature in the Relativistic Jet Source GRS 1915+105
The galactic superluminal source GRS 1915+105 is among the most interesting objects in our Galaxy. It is subject to erratic accretion instabilities with energization of relativistic jets producing X-ray, optical and radio emission. This source was observed by ASCA on Sept. 27, 1994, April 20, 1995, October 23, 1996 and April 25, 1997 as part of a long timescale investigation. We detected strong variability of the source, and in particular the existence of burst/dip structure in October 1996 and April 1997. Clear evidence of transient absorption features at 6.7, 7.0 and 8.0 keV was obtained for the first time in September 1994 and April 1995. Given the phenomenology of plasmoid energization and ejection, these transient spectral features might be produced by material entrained in the radio jets or in other high-velocity outflows. Our contribution to the interpretation is to incorporate these observations into a overall theoretical picture for GRS 1915+105 also taking into account other observations by XTE and BSAX. The emerging picture is complex. The central source is subject to (most likely) super-Eddington instabilities mediated by magnetic field build-up, reconnection and dissipation in the form of blobs that eventually leads to the formation of transient spectral features from the surrounding of the plasmoid emitting region. A comprehensive theoretical investigation is in progress.
Tavani, Marco↗
Eta Carinae: A Tale of Two Periastron Passages
Since 2002, the far-ultraviolet(FUV)flux(1150–1680Å)of Eta Carinae, monitored by the Hubble SpaceTelescope/Space Telescope Imaging Spectrograph, has increased by an order of magnitude. This increase isattributed to partial dissipation of a line-of-sight(LOS)occulter that blocks the central core of the system. Acrossthe 2020 February periastron passage, changes in the FUV emission show a stronger wavelength dependence thanoccurred across the 2003 July periastron passage. Across both periastron passages, most of the FUV spectrumdropped influx then recovered a few months later. The 2020 periastron passage included enhancements of FUVflux in narrow spectral intervals near periastron followed by a transient absorption and recovery to pre-periastronflux levels. The drop influx is due to increased absorption by singly ionized species as the secondary star plungesdeep into the wind of the primary star, which blocks the companion’s ionizing radiation. The enhanced FUVemission is caused by the companion’s wind-blown cavity briefly opening a window to deeper layers of theprimary star. This is thefirst time transient brightening has been seen in the FUV comparable to transientspreviously seen at longer wavelengths. Changes in resonance line-velocity profiles hint that the dissipating occulteris associated with material in LOS moving at−100 to−300 km s−1, similar in velocity of structures previouslyassociated with the 1890s lesser eruption.
Theodore R Gull↗
Double resonance spectroscopy of multiple-photon excited molecules
Multiple infrared photon absorption is a quite general process which molecules can undergo when placed in a high flux of infrared energy, such as the focussed beam of a CO2 laser. In order to understand how this process works, one must be able to follow the evolution of the molecules through their internal states, populated by photon absorption. Double-resonance spectroscopy is the method of a choice for getting at this information. A system pumped by CO2 laser radiation can be examined with a tunable laser probe beam, such as that from a lead-salt diode laser. From such an experiment, one can directly observe Rabi modulation of the absorption lines, determine elementary state-to-state relaxation pathways, and locate higher excited vibrational states. Systems currently under investigation include SF6 and vinyl chloride. In suitable cases, the probe beam can be a tunable visible or UV source, such as a dye laser. Fluorescence spectroscopy can then be used to monitor the transient absorptions produced by multiple-photon excitation. Among the systems which can be examined are biacetyl and glyoxal.
Steinfeld, J. I.↗
Optical and Probe Diagnostics Applied to Reacting Flows
We plan to explore three major threads during the fellowship period. The first interrogates the flame synthesis of carbon nanotubes using aerosol catalysts. Laser light scattering will reveal changes in particle size at various heights above the burner. Analysis of the flame gas by mass spectroscopy will reveal the chemical composition of the mixture. Finally, absorption measurements will map the nanotube concentration within the flow. The second thread explores soot oxidation kinetics. Cavity ring-down absorption measurements of the carbonaceous aerosol can provide a measure of the mass concentration with time and, hence, an oxidation rate. Spectroscopic and direct probe measurements will provide the temperature of the system needed for subsequent modeling. The third thread will explore the details of turbulent flame dynamics. Laser induced incandescence will be applied to measurements of soot volume fraction in a 2-d configuration. Analysis of seed tracer particles by planar laser light MIE scattering will reveal the elemental fuel mixture fraction in the flames. Cavity ring-down spectroscopy, a pulsed transient absorption method, will determine the instantaneous mass loading and its fluctuation. Finally, fluorescence measurements will investigate the formation of PAH's in these flames.
Ticich, Thomas M.↗
Flash photolysis of the charge-transfer band of 1-methylpyridinium, 1-methylcollidinium and 1-methylquinolinium iodides
Optical charge transfer transitions in N-alkyl iodide salts, examining transient absorptions due to flash photolysis
Cozzens, R. F.↗
Pulse radiolysis of epoxy-based matrix materials
Electron beam pulse radiolysis (600 KeV, 3 nsec) experiments have been carried out on epoxy-based matrix materials. Time and wavelength resolved emission and transient absorption techniques as well as ESR studies have been utilized to identify and monitor short lived reactive intermediates resulting from energetic electron impact. An energy deactivation model based on the results of this work has been developed. Recombination of primary charged species is found to be fast, resulting in the formation of longer lived excited electronic states and radicals which control the subsequent energy deactivation.
Coulter, D. R.↗
Fast spectroscopic variations on rapidly-rotating, cool dwarfs. 3: Masses of circumstellar absorbing clouds on AB Doradus
New time-resolved H alpha, Ca II H and K and Mg II h and k spectra of the rapidly-rotating K0 dwarf star AB Doradus (= HD 36705). The transient absorption features seen in the H alpha line are also present in the Ca II and Mg II resonance lines. New techniques are developed for measuring the average strength of the line absorption along lines of sight intersecting the cloud. These techniques also give a measure of the projected cloud area. The strength of the resonance line absorption provides useful new constraints on the column densities, projected surface areas, temperatures and internal turbulent velocity dispersions of the circumstellar clouds producing the absorption features. At any given time the star appears to be surrounded by at least 6 to 10 clouds with masses in the range 2 to 6 x 10(exp 17) g. The clouds appear to have turbulent internal velocity dispersions of order 3 to 20 km/s, comparable with the random velocities of discrete filamentary structures in solar quiescent prominences. Night-to-night changes in the amount of Ca II resonance line absorption can be explained by changes in the amplitude of turbulent motions in the clouds. The corresponding changes in the total energy of the internal motions are of order 10(exp 29) erg per cloud. Changes of this magnitude could easily be activated by the frequent energetic (approximately 10(exp 34) erg) x ray flares seen on this star.
Cameron, A. Collier↗
Photophysical behavior of doubly bridged d7-d7 metal-metal bonded compounds - The crystal structure and the excited- and ground-state electronic spectra of Re2(CO)6(dmpm)2 (dmpm = bis/dimethylphosphino/ methane)
Re2(CO)6(dmpm)2 shows photophysical behavior in a rigid medium that differs dramatically from that observed in fluid solution. In a hydrocarbon glass at 77 K, metal-metal bond homolysis is suppressed and an intense phosphorescence is observed. The transient absorption spectrum, which shows only weak transitions to the red of the ground state 1(sigma-sigma asterisk) transition, permits assignment of the emitting state to a 3(sigma-sigma asterisk) transition. The crystal structure of Re2(CO)6(dmpm)2 is also reported. The ground-state electronic structure is discussed relative to the structural data.
Milder, Steven J.↗
Production of Star-Grazing and Star-Impacting Planetestimals via Orbital Migration of Extrasolar Planets
During the orbital migration of a giant extrasolar planet via ejection of planetesimals (as studied by Murray et al. in 1998), inner mean-motion resonances can be strong enough to cause planetesimals to graze or impact the star. We integrate numerically the motions of particles which pass through the 3:1 or 4:1 mean-motion resonances of a migrating Jupiter-mass planet. We find that many particles can be trapped in the 3:1 or 4:1 resonances and pumped to high enough eccentricities that they impact the star. This implies that for a planet migrating a substantial fraction of its semimajor axis, a fraction of its mass in planetesimals could impact the star. This process may be capable of enriching the metallicity of the star at a time when the star is no longer fully convective. Upon close approaches to the star, the surfaces of these planetesimals will be sublimated. Orbital migration should cause continuing production of evaporating bodies, suggesting that this process should be detectable with searches for transient absorption lines in young stars. The remainder of the particles will not impact the star but can be ejected subsequently by the planet as it migrates further inward. This allows the planet to migrate a substantial fraction of its initial semimajor axis by ejecting planetesimals.
Quillen, A. C.↗
Vibrational self-quenching rates of CO(v=1,2) measured via transient diode laser absorption spectroscopy
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Cole J. Hediger↗
Spectroscopic, orbital, and physical properties of the binary Feige 24 and detection of transient He II absorption in the system
We have obtained new high-dispersion optical spectroscopy at Kitt Peak National Observatory (KPNO) and new International Ultraviolet Explorer (IUE) spectroscopy of the white dwarf+red dwarf binary system Feige 24. The optical range shows a composite DA+dM spectrum, together with H I Balmer and He I emission. The orbital phase dependence of the emission shows that it results from extreme ultraviolet (EUV) light reprocessing in the red dwarf upper atmosphere. The systems close enough and hot enough to show this reprocessing signature only recently emerged from common-envelope evolution. The ultraviolet spectrum exclusively emanates from the white dwarf and shows numerous heavy element absorption lines. We measured accurate radial velocities of the red dwarf component motion, traced by both optical absorption and emission lines, and new radial velocities of the white dwarf, traced by ultraviolet Fe V lines. Combining these measurements, we refined the orbital parameters presented by Vennes et al. (1991), and we confirmed that the white dwarf gravitational redshift is exceptionally small with 9 +/- 2 km/s. From this we deduced that the interior is either pure helium or carbon with a thick hydrogen layer, and we derived, for the combined interior compositions, a white dwarf mass and radius of M(sub WD) = 0.44-050 solar mass and R(sub WD) = 0.028-0.036 solar radius. We suggest that Feige 24 could be a typical case of close binary evolution leading to the formation of a low-mass helium white dwarf. The mass of the red dwarf and the inclination of the system naturally follow: M(sub dM) = 0.26-0.33 solar mass, i greater than or equal to 75 deg. High-dispersion H-alpha line profiles are asymmetrical, strongly enhanced toward the blue, suggesting a moving atmosphere possibly linked to a mass loss rate of 10(exp -10) solar mass/yr. The IUE spectra taken when the system is near inferior conjunction show strong He II 1640 A absorption. The profile is highly variable in width and intensity. Because it is correlated with the passage of the white dwarf at inferior conjunction, the absorption may occur in some foreground plasma emanated by the red dwarf and accumulating near a Lagrangian point or, alternatively, it may originate in an accretion spot on the white dwarf surface coaligned with the major orbital axis. Either way, the He II detection may imply substantial mass loss from the red dwarf with a corollary reclassification of Feige 24 as a mixed He/H DAO white dwarf resulting from accretion of secondary mass-loss material. Feige 24 is the prototype of a class of young, EUV-emitting, binary systems comprising a late main sequence secondary and a hot H-rich white dwarf; the class is characterized by optical and ultraviolet photospheric He II absorption, circumstellar C IV lambda (1550) absorption, and by the presence of EUV-induced, phase-dependent Balmer fluorescence. These young systems present the best opportunity to constrain theory of common-envelope evolution.
Vennes, Stephane↗