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At least 145 records · Page 8

Photodissociation yields of CS2 at 1060-1520 A

Photoabsorption and fluorescence cross sections of CS2 were measured in the 1060-1520 A region using synchrotron radiation in order to provide information needed for modeling the CS abundance in the interstellar medium. The absorption in the 1060-1200 A region is smooth and continuous, except for the presence of a strong absorption band at 1117 A, while for wavelengths longer than 1200 A, the absorption spectrum shows the structure of Rydberg states. The fluorescence in the 1900-3000 A region begins to appear at 1335 A, and is mainly the CS(A 1Pi-Chi 1Sigma +) transition in the 2400-2800 A region. The fluorescence in the 1900-8000 A region begins to appear at 1490 A, and, in addition to the previous transition, is composed of the transitions of S(1S0-3P1) at 4589 A and of CS(d 3 Delta, a-prime 3Sigma +, and a 3Pi-Chi 1Sigma +) at 3000-4000 A. The quantum yields for the production of fluorescence are determined to have maxima of 13 and 7.5% at 1235 A for the fluorescence in the 1900-8000 and 1900-3000 A regions, respectively.

Day, R. L.↗

Fluorescence yields from photodissociation of OCS at 1060-1240 A

The cross sections for the production of fluorescence (3000-8000 A) from excited photofragments of OCS were determined in order to gain a better understanding of the role of carbonyl sulfide in interstellar photochemistry. Synchrotron radiation was used as the light source for the measurements in the 1060-1240 A region, as it is suitable for measuring the absorption cross section in the structured region. It was found that the quantum yields for the production of various CO triplet states are less than 1.5% at the observed excitation photon wavelengths.

Lee, L. C.↗

Photodissociation of NH3 at 106-200 nm

The absorption and fluorescence cross sections for NH3 are measured in the 106-200 nm region using synchrotron radiation as the light source. The threshold wavelengths for the production of the NH (b to X) and NH (c to a) emissions from NH3 dissociation are measured and compared with previous measurements. The heat of formation of NH determined from these thresholds agrees well with the value determined from thermochemical data. The process of dissociation of NH3 into NH2(2AL) and H2(S) has a significant quantum yield whose maximum at 134 nm is about twice the NH(c) production yield. All the vibronic levels of the B and C states produce the NH2(2A1) emission, contrary to previous theoretical interpretations.

Suto, M.↗

Application of an InGaAsP diode laser to probe photodissociation dynamics - I(asterisk) quantum yields from n- and i-C3F7I and CH3I by laser gain vs absorption spectroscopy

Initial measurements on I-asterisk yields of alkyl iodides at 266 nm are reported using gain vs. absorption spectroscopy with an InGaAsP diode probe laser. The results are 102 percent + or - 4 percent, 102 percent + or - 7 percent, and 73 percent + or - 4 percent for n-C3F7I, i-C3F7I, and CH3I respectively. Future prospects for the development of diode laser systems and for their use in dynamical studies are discussed.

Hess, W. P.↗

Photodissociation of metastable O2(a 1 Delta g): Implications for stratospheric O3

The potential energy curves of Saxon and Liu (1977) are used to calculate nuclear radial wave functions for O2 in the a 1 Delta g and C 3 Delta u states. Franck-Condon factors are evaluated for both bound-bound and bound-free transitions. Observational values for the radiative lifetimes of discrete vibrational levels of the C 3 Delta u state are used to place constraints on the cross section for photodissociaation of a 1 Delta g. It is argued that the cross section for the dissociation of O2(a 1 Delta g) through the C 3 Delta u state is smaller by four orders of magnitude than values required by Frederick and Cicerone (1985) to resolve the apparent discrepancy between computed and measured concentrations for O3 in the upper atmosphere.

Dalgarno, A.↗

Photoabsorption and photodissociation of molecules important in the interstellar medium

A windowless apparatus was constructed and used to measure the photoabsorption and fluorescence cross sections of molecules in the extreme ultraviolet region. Photoabsorption and fluorescence cross sections of H2O, D2O, H2S, D2s, and Co were measured in the 50 to 200 nm region. These quantitative data are currently needed for the determination of the formulation and destruction rates of molecules in the interstellar medium.

Lee, Long C.↗

Photoabsorption and photodissociation of molecules important in the interstellar medium

Photoabsorption and fluorescence cross sections of molecules important in the interstellar medium were measured in the 90 to 200 nm region using synchrotron radiation, excimer laser, and condensed discharge lamps as light sources. The quantitative spectroscopic data are currently needed for the modeling of formation and destruction rates of molecules by the interstellar radiation field. Fluorescences from excited photofragments produced by vacuum ultraviolet radiation of molecules are dispersed to identify the emitting species. The fluorescence data are useful for the identification of emission sources in interstellar clouds.

Lee, Long C.↗

CH3O(A-X) fluorescence from photodissociation of dimethyl ether

The paper reports the quantitative photoabsorption and fluorescence cross sections of dimethyl ether (DME) measured with synchrotron radiation. Determinations were also made of the absolute fluorescence cross sections, the fluorescence quantum yield, and the radiative lifetime.

Suto, Masako↗

Fluorescence yields from photodissociative excitation of HCOOH, HCOOCH3, and CH3COOH in the vacuum-ultraviolet region

The photoexcitation processes of HCOOH, HCOOCH3, and CH3COOH were studied in the vacuum-ultraviolet region by using synchroton radiation and a pulsed discharge lamp as light sources. The absorption and fluorescence cross sections of these molecules were measured in the 106-250-nm region. Fluorescences were detected from photoexcitation of HCOOH and HCOOCH3, but not from CH3COOH. Fluorescence produced at 123.9 nm was dispersed and identified as the excited OH and HCOO radicals. Fluorescence quantum yields of HCOOH and HCOOCH3 increase with decreasing excitation wavelengths with maxima of 5 and 0.3 percent at 106 nm, respectively.

Suto, Masako↗

Laboratory studies of photodissociation processes relevant to the formation of cometary radicals

The strength of the C2(d 3 Pi g yields a 3 Pi u) Swan band emission in the spectra of cometary comae identifies this species as a prominent constituent of the coma gas. It was previously suggested that the formation of cometary C2 proceeds via the secondary photolysis of the C2H radical. The detection of C2H in the interstellar medium and the recent analysis of the radial variation in C2(delta V=O) surface brightness of Comet Halley support the postulate that C2 is a third-generation molecule. Measurement of the C2 and C2H translational energy distributions produced from the multiphoton dissociation (MPD) of acetylene at 193 nm are identified . Time-resolved FTIR emission studies of the nascent C2H radical formed in the C2H2 yields C2H + H reaction verify that this species is produced both vibrationally and electronically excited. A survey of the internal energy distributions of the C2 fragments produced from the MPD of acetylene using a high intensity ArF laser is currently in progress in the laboratory. Recent experiments have focused on the measurement of rotational energy distribution for the C2(A 1 Pi u, a 3 Pi u) fragments. The C2(a 3 Pi u) detection capability is currently being improved by performing this experiment in a molecular beam, thus allowing for discrimination between initial emission and laser-induced fluorescence (LIF). Although the experiments performed to date provide considerable evidence in support of C2H yields C2 + H reaction, there is an important distinction to be made when comparing the laboratory conditions to those typically found in comets. The C2H radicals generated in the laboratory experiments are formed vibrationally and/or electronically excited. Any rotationally/vibrationally excited C2H present in cometary comae will quickly undergo radiative relaxation in the infrared to their lowest rotational and vibrational state. Experiments are currently under way to confirm the cometary formation of C2 via the VUV dissociation of cold C2H.

Urdahl, R. S.↗

Rapid calculation of radiative heating rates and photodissociation rates in inhomogeneous multiple scattering atmospheres

The solution of the generalized two-stream approximation for radiative transfer in homogeneous multiple scattering atmospheres is extended to vertically inhomogeneous atmospheres in a manner which is numerically stable and computationally efficient. It is shown that solar energy deposition rates, photolysis rates, and infrared cooling rates all may be calculated with the simple modifications of a single algorithm. The accuracy of the algorithm is generally better than 10 percent, so that other uncertainties, such as in absorption coefficients, may often dominate the error in calculation of the quantities of interest to atmospheric studies.

Toon, Owen B.↗

Physical conditions in photodissociation regions - Application to galactic nuclei

A procedure is outlined which determines the physical characteristics of the neutral interstellar medium in the nuclei of luminous galaxies. The method uses millimeter and IR observations to find the mass and density of the molecular and atomic gas components as well as the UV flux incident on clouds. The area and volume filling factors and approximate number of clouds and cloud radii are also found. For the Galactic center, about 100 clouds of radius about 0.4 pc and density about 100,000/cu cm are found within about 5 pc. The atomic gas temperature is about 700 K and the FUV field on clouds is about 100,000 times the local Galactic FUV field. The flux is consistent with a central source of luminosity of 2-3 x 10 to the 7th solar. Roughly 100,000 clouds of radius roughly 0.4 pc are found within the roughly 330 pc nuclear region of M82. The large number of clouds produces a projected area filling factor approaching unity. Cloud heating may be dominated by an intense interstellar UV flux.

Wolfire, Mark G.↗

Laser studies of the photodissociation dynamics of cometary radicals

In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.

Jackson, William M.↗

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photo absorption, photo dissociation, and fluorescence cross sections of interstellar molecules and radicals were measured in the vacuum ultraviolet region. These quantitative optical data are useful for understanding of the formation and destruction processes of molecules under the intense interstellar W radiation field. Infrared (IR) emissions from W excitation of aromatic molecules were also observed in this research program. The research results are useful for studying the sources of the 'unidentified' interstellar infrared (UIR) emission bands.

Lee, Long C.↗

Photodissociation of O2 and H2O in the middle atmosphere: Comparison of numerical methods and impact on model O3 and OH

We have compared three photochemical diurnal models of O3 and OH in the upper stratosphere and mesosphere which use different techniques for calculating the absorption of solar ultraviolet radiation by the O2 Schumann-Runge bands. One model uses a detailed line-by-line representation of the O2 cross section from 1750-2050 A, while the two others use lower resolution, parameterized cross sections. Using the parameterized cross sections, the calculated O3 profiles for both day and night agree with those obtained from the line-by-line model to within 6%. This appears to eliminate inaccuracies in the parameterized O2 cross section as a major cause of previously reported model O3 deficits. A portion of the residual differences from the line-by-line model are attributed to inaccuracies in the calculated H2O photolysis rate. A parameterized H2O cross section is offered which improves the accuracy of this calculation.

Siskind, David E.↗

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.↗

Photodissociation Cross Sections for the Production of C2 from C2H Using Laser Induced Hg Photosensitization and Tunable Ultraviolet and Visible Lasers

The principle goal of our research was to understand the formation of free radicals in comets. To do this we compared laboratory results with cometary observations in attempt to make sure that the cometary observations agree with what is known about the photochemistry of the proposed parent molecule. Initially we concentrated on the CS emission in an effort to show the parent of this molecule was CS2, consistent with cometary observations of the photochemical lifetime. We then started to look into the problem of the C2 formation in comets. We set out to see if we could measure all of the nascent distributions of the C2 products in the hope that they would be a characteristic signature of the formation process.

Jackson, William M.↗