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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Photodissociation processes in the OH molecule

The potential energy curves of several excited states of OH of 2Sigma(+), 2Sigma(-), 2Pi, and 2Delta symmetries, and the transition moments connecting the excited states with the ground state and with each other, are calculated using two previously published theoretical models. The importance of the excited states in photodissociation is explored. Direct photodissociation by absorption into repulsive electronic states, as well as the contribution of absorption into bound electronic states, are discussed. Because they may participate in the photodissociation processes, several quartet states and one of the sextet spin multiplicity are investigated. The mechanism by which bound states can be dissociated are considered and estimates of the dissociation efficiencies of the mechanisms are made. Absorption into the bound 3 2Pi state may be an important dissociation channel. It is shown that OH is dissociated by the absorption of Lyman alpha radiation, a channel of particular significance in shocked interstellar gas and in cometary atmospheres.

Van Dishoeck, E. F.↗
NASA NTRS1985

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photoabsorption and photodissociation cross sections of several interstellar molecules and radicals in the 105 to 210 nm region were measured. The research results accomplished are briefly described. Photoabsorption cross sections of OD and CN, and photoabsorption and photodissociation of HCl, and photoabsorption and photodissociation cross sections of CH3OH are discussed.

Lee, L. C.↗
NASA NTRS1985

Photodissociation rates of OH, OD, and CN by the interstellar radiation field

The photoabsorption cross sections for OH, OD, and CN in the vacuum ultraviolet region are measured. The cross sections for the hydroxyl radicals are of the order of 10 to the -17th sq cm, but the photoabsorption for CN is so low that only an upper limit of 2 x 10 to the -18th sq cm is obtained. The molecular photodissociative processes are discussed. The photodissociation cross sections are inferred from the photoabsorption cross sections. On the basis of the measured data, the photodissociation rates by the interstellar radiation field are computed and discussed.

Nee, J. B.↗
NASA NTRS1985

Photoabsorption cross section of CH3CN - Photodissociation rates by solar flux and interstellar radiation

The photoabsorption cross section of CH2CN vapor was measured in the 106-180 nm region using synchrotron radiation as a light source. The cross section and the quantum yield for the production of CN (A, B-X) fluorescence were measured and were used to infer the photodissociation cross section of CH3CN. The cross sections were used to calculate the photodissociation rates of CH3CN by the solar flux and by the interstellar radiation. In both the stratosphere and the troposphere, the solar photodissociation of CH3CN is negligible in comparison with chemical degradation.

Suto, M.↗
NASA NTRS1988

OH(A-X) fluorescence from photodissociative excitation of HO2 at 157.5 nm

The OH(A-X) fluorescence from photodissociative excitation of HO2 by F2 laser photons (157.5 nm) was observed and compared with the OH fluorescence spectra of H2O2 and the O2+CH3OH mixture. The rotational population distributions of OH(A) were obtained from the fluorescence spectra. The most populated levels are J = 4 for photodissociative excitation of HO2, J = 20 for H2O2, and J = 21 for the O2+CH3OH mixture. The fluorescence from the gas mixture is attributed to the O + H recombination for which the atoms are produced from photodissociation of parent molecules.

Suto, M.↗
NASA NTRS1988

The photodissociation and chemistry of interstellar CO

Recent work on the vacuum UV absorption spectrum of CO to the description of the photodissociation of interstellar CO and its principal isotopic varieties is discussed. The effects of line broadening, self-shielding, shielding by H and H2, and isotope-selective shielding are examined as functions of depth into interstellar clouds. The photodissociation rates of the isotopic species are larger than that of (C-12)O inside the clouds by up to one to two orders of magnitude. A simple approximation to the attenuation by line absorption is given in tabular form. Computed abundances of CO and related species C and C+ are presented for a variety of interstellar clouds ranging from diffuse clouds to dense photodissociation regions. Several series of models of translucent clouds are presented which illustrate how the CO abundance increases rapidly with total cloud thickness. The variations of the isotopic abundances with depth and their sensitivity to temperature and total cloud thickness are explored in detail.

Van Dishoeck, Ewine F.↗
NASA NTRS1989

Photodissociation of CO in the thermosphere of Venus

Recent investigations of CO photoabsorption demonstrate that photodissociation longward of the ionization threshold at 88.5 nm occurs primarily through line absorptions rather than continuous processes. High-resolution photoabsorption cross sections for CO at rotational temperatures near 250 K have been constructed from the improved data on dissociating transitions. The effects of the new cross sections on the rate of solar photodissociation of CO in the thermosphere of Venus are examined, and the results are compared to values obtained with the lower resolution cross sections available previously. It is found that the photodissociation profile peaks slightly higher in the atmosphere and the peak value and integrated total rate both decrease by about a factor of two.

Fox, J. L.↗
NASA NTRS1990

Photodissociation of Cl2O2 in the spring Antarctic lower stratosphere

The likely photodissociation pathways of chlorine peroxide are examined. Reasoning by analogy between hydrogen peroxide and chlorine peroxide, it is shown that photodissociation of chlorine peroxide at wavelengths longer than 250 nm is not likely to give chlorine atoms as a primary product. Reasoning by analogy with molecules whose visible spectra are known, it is concluded that chlorine peroxide is also likely to photodissociate in the visible to give ClO radicals as primary products.

Eberstein, Igor J.↗
NASA NTRS1990

Physical conditions in photodissociation regions: Application to galactic nuclei

Infrared and sub-millimeter observations are used in a simple procedure to determine average physical properties of the neutral interstellar medium in Galactic photodissociation regions as well as in ensembles of clouds which exist in the nuclei of luminous infrared galaxies. The relevant observations include the Infrared Astronomy Satellite (IRAS) infrared continuum measurements, infrared spectroscopy of the fine-structure lines of SiII 35 microns, OI 63 microns, and CII 158 microns, and the 2.6 mm CO (J=1-0) rotational transition. The diagnostic capabilities of the OI 145 microns line is also addressed. Researchers attribute these emission lines as well as the continuum to the atomic/molecular photodissociation region on the surfaces of molecular clouds which are illuminated by strong ultraviolet fields. They use the theoretical photodissociation region models of Tielens and Hollenbach (1985, Ap. J., 291, 722) to construct simple diagrams which utilize line ratios and line to continuum ratios to determine the average gas density n, the average incident far-ultraviolet flux G sub o, and the temperature of the atomic gas T.

Wolfire, M. G.↗
NASA NTRS1990

Photodissociation regions

Photodissociation regions are interstellar regions of predominantly neutral gas where the FUV radiation field plays a significant role in the chemistry and/or the heating. Photodissociation, grain attenuation of the FUV flux and grain photoelectric heating lead to copious emission of C II (158 microns), O I (63 microns), Si II (35 microns), C I (370,609 microns), H2 vibrotational and CO rotational transitions, and IR continuum. Theoretical models compared with observations diagnose such physical parameters as the density and temperature structure, the elemental abundances, and the FUV radiation field. Applications are made to Orion, M17 and galactic nuclei. Theoretical photodissociation models can explain the correlation in the C II (158 microns) and CO J = 1-0 emission and the correlation of the CO J = 1-0 luminosity with the molecular mass. Theoretical models also point to feedback mechanisms which may control the rate of star formation in galaxies and which may regulate the column density through giant molecular clouds.

Hollenbach, David J.↗
NASA NTRS1992

Velocity distributions of H and OH produced through solar photodissociation of H2O

The calculated velocity distributions of atomic hydrogen and hydroxyl radicals produced through solar photodissociation of gaseous water molecules are presented. Under collisionless conditions, the calculation was carried out using the most recent available data for the production of H and OH through photodissociation of H2O from its dissociation onset throughout the EUV region. Because the lack of data in certain spectral regions, only upper and lower bounds to the velocity distributions can be obtained. The results show that the H atoms and OH radicals produced exhibit multiple velocity groups. Since most of the current cometary modeling uses a single velocity of 20 km/s associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of cometary atomic hydrogen.

Wu, C. Y. Robert↗
NASA NTRS1993

Velocity distributions of hydrogen atoms and hydroxyl radicals produced through solar photodissociation of water

The velocity distributions of H and OH fragments produced through solar photodissociation of gaseous H2O molecules under collisionless conditions are presented. The calculations are carried out using: the most recently available absolute partial cross sections for the production of H and OH through photodissociation of H2O from its absorption onset at 1860 A down to 500 A; the newly available vibrational and rotational energy distributions of both the excited and ground state OH photofragments; the calculated cross sections for the total dissociation processes; and the integrated solar flux in 10 A increments from 500 to 1860 A in the continuum regions and the specific wavelength and flux at the bright solar lines. The calculated results show that the H atoms and the OH radicals produced exhibit multiple velocity groups. Since most current cometary modeling uses a single velocity of 20 km/sec associated with the photodissociation of H2O, the present results may be useful in interpreting the many peaks observed in the velocity distributions of the H Lyman alpha and H alpha of comets.

Wu, C. Y. R.↗
NASA NTRS1994

Carbon recombination lines as a diagnostic of photodissociation regions

We have observed the C91 alpha radio recombination line toward the Orion H II region. This narrow (approximately 3-5 km per sec full width at half maximum (FWHM)) line is spatially very extended (approximately 8 arcmin or 1 pc). These charateristics compare well with the observed characteristics of the C II fine structure line at 158 microns. Thus, the C91 alpha line originates in the predominantly neutral photodissociation regions separating the H II region from the molecular cloud. We have developed theoretical models for the C II radio recombination lines from photodissociation regions. The results show that the I(C91 alpha)/I(C158) intensity ratio is a sensitive function of the temperature and density of the emitting gas. We have also extended theoretical models for photodissociation regions to include the C II recombination lines. Comparison with these models show that, in the central portion of the Orion region, the C91 alpha line originates in dense (10(exp 6) per cu cm), warm (500-1000 K) gas. Even at large projected distances (approximately 1 pc), the inferred density is still high (10(exp 5) per cu cm) and implies extremely high thermal pressures. As in the case of the (C II) 158 microns line, the large extent of the C91 alpha line shows that (FUV) photons can penetrate to large distances from the illuminating source. The decline of the intensity of the incident radiation field with distance from Theta(sup 1) C seems to be dominated by geometrical dilution, rather than dust extinction. Finally, we have used our models to calculate the intensity of the 9850 A recombination line of C II. The physical conditions inferred from this line are in good agreement with those determined from the radio recombination and the far-infrared fine-structure lines. We show that the ratio of the 9850 A to the C91 alpha lines is a very good probe of very high density clumps.

Natta, A.↗
DOE OSTI2020

Photodissociation dynamics of the tert -butyl perthiyl radical

Here, the photodissociation dynamics of the tert-butyl perthiyl (t-BuSS) radical are investigated by fast-beam coincidence translational spectroscopy. A fast (6 keV-8 keV) beam of neutral t-BuSS radicals is produced via photodetachment of the corresponding anion, followed by photodissociation at 248 nm (5.00 eV) or 193 nm (6.42 eV) and coincident detection of the neutral products. Photofragment mass and translational energy distributions are obtained at both wavelengths. At 248 nm, the dominant product channel (90%) is found to be S loss, with a product translational energy distribution that peaks close to the maximum available energy and an anisotropic photofragment angular distribution, indicating dissociation along a repulsive excited state. A minor channel (10%) leading to the formation of S 2 + t-Bu is also observed. At 193 nm, both two- and three-body dissociation are observed. The formation of S 2 + t-Bu is the dominant two-body product channel, with multiple electronic states of the S 2 molecule produced via excited-state dissociation processes. The formation of S + t-BuS is a minor two-body channel at this dissociation energy. The three-body channels are S 2 + H + isobutene, S 2 + CH 3 + propene, and S + SH + isobutene. The first two of these channels result from a sequential dissociation process in which the loss of S 2 from t-BuSS results in ground-state t-Bu with sufficient internal energy to undergo secondary fragmentation. The third three-body channel, S + SH + isobutene, is attributed to the loss of internally excited HS 2 from t-BuSS, which then rapidly dissociates to form S + SH in an asynchronous concerted dissociation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exploring direct photodetachment and photodissociation–photodetachment dynamics of platinum iodide anions (PtI n - , n = 2–5) using cryogenic photoelectron spectroscopy

The direct photodetachment and two-photon photodissociation–photodetachment processes of a series of PtI n - (n = 2–5) anions were systematically studied using cryogenic anion photoelectron spectroscopy and first-principles electronic structure calculations. The adiabatic/vertical detachment energies (ADEs/VDEs) of these anions were determined from their 193 nm photoelectron (PE) spectra, i.e., 3.54/3.63, 4.04/4.09, 4.33/4.36, and 4.37/4.41 eV for n = 2–5, respectively, and well reproduced by B3LYP-D3(BJ)/aug-cc-pVTZ-pp calculations. As the coordination number increases, the electron affinity (EA) of PtI n • (n = 2–5) neutrals (equivalent to the corresponding anion’s ADE) gradually increases, exceeding the EA of Cl at n = 3 and exhibiting superhalogen characteristics for n ≥ 3. Meanwhile, the ground state transition contributed from detaching electrons in the highest occupied molecular orbital gradually evolves from the central metal Pt to the iodine ligands. For the PtI 3 - anion, besides one-photon direct detachment, four distinct two-photon photodissociation–photodetachment channels were identified, and the competition between them was discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Investigating the ultraviolet photodissociation of bromocyclopropane with ultrafast electron diffraction

We have studied the photodissociation of gas-phase bromocyclopropane by 200 nm wavelength ultraviolet radiation using ultrafast electron diffraction. Bromocyclopropane is a prototypical molecule in the study of organobromides, a class of molecules that have a significant impact on atmospheric ozone depletion through their photochemistry. Here, previous studies have revealed two possible reaction pathways for the photodissociation of bromine from bromocyclopropane; either the C–Br bond dissociates, leaving behind a cyclopropyl ring, or there is a concerted opening of the cyclopropyl ring along with the C–Br bond dissociation. In this work, both our experimental and simulation results indicate that the majority of the UV-photoexcited BCP molecules (88% ± 11% in the experiment) follow the first reaction pathway, in which the cyclopropyl ring remains closed after homolytic C–Br bond cleavage. This direct bond dissociation occurs within the experimental time resolution of 270 fs. In order to differentiate between the possible reaction end-products, both of which have diffraction signals dominated by the bromine atom, a new analysis method has been employed, which is more sensitive to the structure of the end-products.

Atmospheric chemistry↗
DOE OSTI2021

Photodissociation of dicarbon: How nature breaks an unusual multiple bond

The dicarbon molecule (C2) is found in flames, comets, stars, and the diffuse interstellar medium. In comets, it is responsible for the green color of the coma, but it is not found in the tail. It has long been held to photodissociate in sunlight with a lifetime precluding observation in the tail, but the mechanism was not known. Here we directly observe photodissociation of C 2 . From the speed of the recoiling carbon atoms, a bond dissociation energy of 602.804(29) kJ∙mol -1 is determined, with an uncertainty comparable to its more experimentally accessible N 2 and O 2 counterparts. The value is within 0.03 kJ∙mol -1 of high-level quantum theory. This work shows that, to break the quadruple bond of C 2 using sunlight, the molecule must absorb two photons and undergo two “forbidden” transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗