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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Photodissociation of pernitric acid (HO2NO2) at 248 nm

The photodissociation of pernitric acid (PNA) was studied at 248 nm. The quantum yield for production of OH radicals is 34 + or - 16 percent. The yield of OH from PNA was measured relative to that of H2O2. The translational and rotational energy content of the OH photofragment from PNA was characterized. A fluorescent emission was also observed and characterized. It is attributed to electronically excited NO2 produced in the PNA photodissociation. A maximum yield of 30 percent for NO2 production was determined. The intensity of this emission, and a mass spectrometric peak at m/e = 33, were found to be useful means of characterizing the purity of the PNA sample.

Macleod, Helene↗
NASA NTRS1988

C II 158 micron and O I 63 micron observations of NGC 7023 - A model for its photodissociation region

Emission in the far IR fine-structure lines of O I (63 microns) and C II (158 microns) from the bright optical reflection nebula NGC 7023 has been observed. It is suggested that this emission arises in a warm, atomic photodissociation region produced by the interaction of the UV radiation of the illuminating star with a molecular cloud. The density and temperature in the photodissociation region is estimated and a model for the region is constructed.

Chokshi, A.↗
NASA NTRS1989

IR line emission from dense photodissociation regions

The results of the study on the molecular and fine structure line emission, from dense photodissociation regions, are discussed. The work is focused on the prediction of the line emission from CO and H2 molecules. It is found that, when the gas density is sufficiently high, self-shielding of the molecules can move the C(+)/CO and H/H2 transitions close to the surfaces of the molecular cloud where they can feel the full effect of heating by the ultraviolet radiation field. Collisional de-excitation of the H2 can move the lower levels towards low temperature emission producing an apparently shocked line ratio for two low-J levels, while the high-J levels retain a fluorescent value. Appreciable emission in high-J CO molecules originates in this warm molecular gas. Comparison with observation suggests that high density clumps are a common phenomena in photodissociation regions.

Burton, M.↗
NASA NTRS1989

A 10-watt CW photodissociation laser with IODO perfluoro-tert-butane

NASA has been investigating the feasibility of direct solar-pumped laser systems for power beaming in space. Among the various gas, liquid, and solid laser systems being proposed as candidates for solar-pumped lasers, the iodine photodissociation gas laser has demonstrated its potential for space application. Of immediate attention is the determination of system requirements and the choice of lasants to improve the system efficiency. The development of an efficient iodine laser depends on the availability of a suitable iodide which has favorable laser kinetics, chemically reversibility, and solar energy utilization. Among the various alkyliodide lasants comparatively tested in a long-pulse system, perfluoro- tert-butyl iodide, T-C4F9I, was found to be the best. However, the operating conditions for the laser medium in a continuously pumped and continuous-flow iodine laser differ considerably from those in the pulsed regime. The results of the continuous wave (CW)) laser performance from t-C4F9I are reported. Perfluoro- n-propyl iodide, n-C3F7I is used for comparison because of its universal use in photodissociation iodine lasers.

Tabibi, Bagher↗
NASA NTRS1990

Line emission from clumpy photodissociation regions

A theoretical parameter study of dense photodissociation regions is presented. It is found that when the gas density is sufficiently high relative to the FUV flux, self-shielding of the molecules can move the C(+)/CO and H/H2 atomic-molecular transitions close to the surfaces of the molecular cloud, where they can feel the full effect of heating by the FUV radiation field. For n of 100,000/cu cm, collisional deexcitation of the FUV-pumped H2 can move the lower levels toward the LTE, producing line ratio resembling those of shocked regions for these low-v levels, while the high-v level line ratios retain a 'fluorescent' value. Appreciable emission in high-J transitions of CO originates in this warm molecular gas. Comparison with observations suggests that a small volume filling factor of high density clumps embedded within a moderate density interclump medium are a common phenomenon in photodissociation regions.

Burton, Michael G.↗
NASA NTRS1991

The states of carbon and nitrogen atoms after photodissociation of CN, CH, CH(+), C2, C3, and CO in comets

The photodissociation of carbon compounds by solar UV radiation at a heliocentric distance of 1 AU is examined, comparing published observational data with the predictions of theoretical models and results from laboratory experiments. It is shown that species other than CO, including CN, CH, CH(+), C2, and C3, can contribute to the observed brightness of the VUV lines of C I (156.1, 165.7, and 193.1 nm) and C II (133.5 nm) in comet comae. CN photodissociation is also found to produce metastable 2D0 and 2P0 N I atoms, possibly leading (at heliocentric distances less than 0.25 AU) to 143.9-nm emission via resonance fluorescence.

Singh, P. D.↗
NASA NTRS1992

Photodissociation of CH2. I - Potential energy surfaces of the dissociation into CH and H

The possible photodissociation pathways of the CH2 radical are studied using ab initio multireference configuration-interaction methods, and accurate photodissociation cross sections and branching ratios for the production of CH + H and C + H2 are obtained. Potential energy surfaces were calculated using the Wuppertal-Bonn self-consistent field plus a multireference single and double-excitation configuration interaction package of programs. Two-dimensional potential energy surfaces of the ten lowest triplet states correlating with the seven lowest states of CH were calculated as functions of bond angle and one C-H bond distance, keeping the other C-H bond distance fixed at the equilibrium CH2 value.

Bearda, Robert A.↗
NASA NTRS1993

Nova dust nucleation - Kinetics and photodissociation

Dust is observed to form in nova ejecta. The grain temperature is determined by the diluted nova radiation field rather than the gas kinetic temperature, making classical nucleation theory inapplicable. We used kinetic equations to calculate the growth of carbon nuclei in these ejecta. For expected values of the parameters too many clusters grew, despite the small sticking probability of atoms to small clusters, and the clusters only reached radii of about 100 A when the carbon vapor was depleted. We then included the effects of cluster photodissociation by ultraviolet radiation from the nova. This suppresses nucleation, but too well, and no grains form at all. Finally we suggest that a few growing carbon nuclei may be protected from photodissociation by a sacrificial surface layer of hydrogen.

Johnson, D. J.↗
NASA NTRS1995

Quantum yield for carbon monoxide production in the 248 nm photodissociation of carbonyl sulfide (OCS)

Tunable diode laser absorption spectroscopy has been coupled with excimer laser flash photolysis to measure the quantum yield for CO production from 248 nm photodissociation of carbonyl sulfide (OCS) relative to the well-known quantum yield for CO production from 248 nm photolysis of phosgene (Cl2CO2). The temporal resolution of the experiments was sufficient to distinguish CO formed directly by photodissociation from that formed by subsequent S((sup 3)P(sub J)) reaction with OCS. Under the experimental conditions employed, CO formation via the fast S((sup 1)D(sub 2)) + OCS reaction was minimal. Measurements at 297K and total pressures from 4 to 100 Torr N2 + N2O show the CO yield to be greater than 0.95 and most likely unity. This result suggests that the contribution of OCS as a precursor to the lower stratospheric sulfate aerosol layer is somewhat larger than previously thought.

Zhao, Z.↗
NASA NTRS1997

[Photodissociation of Acetylene and Acetone using Step-Scan Time-Resolved FTIR Emission Spectroscopy]

The photodissociation of acetylene and acetone was investigated as a function of added quenching gas pressures using step-scan time-resolved FTIR emission spectroscopy. Its main components consist of Bruker IFS88, step-scan Fourier Transform Infrared (FTIR) spectrometer coupled to a flow cell equipped with Welsh collection optics. Vibrationally excited C2H radicals were produced from the photodissociation of acetylene in the unfocused experiments. The infrared (IR) emission from these excited C2H radicals was investigated as a function of added argon pressure. Argon quenching rate constants for all C2H emission bands are of the order of 10(exp -13)cc/molecule.sec. Quenching of these radicals by acetylene is efficient, with a rate constant in the range of 10(exp -11) cc/molecule.sec. The relative intensity of the different C2H emission bands did not change with the increasing argon or acetylene pressure. However, the overall IR emission intensity decreased, for example, by more than 50% when the argon partial pressure was raised from 0.2 to 2 Torr at fixed precursor pressure of 160mTorr. These observations provide evidence for the formation of a metastable C2H2 species, which are collisionally quenched by argon or acetylene. Problems encountered in the course of the experimental work are also described.

McLaren, Ian A.↗
NASA NTRS2002

Photoevaporation of Clumps in Photodissociation Regions

We present the results of an investigation of the effects of Far Ultraviolet (FUV) radiation (6.0eV < hv < 13.6eV) from hot early type OB stars on clumps in star-forming molecular clouds. Clumps in FUV-illuminated regions (or photodissociation regions or PDRs) undergo external heating and photodissociation as they are exposed to the FUV field, resulting in a loss of cold, molecular lump mass as it is converted to warm atomic gas. The heating, if rapid, creates strong photoevaporative mass flows off the clump surfaces, and drives shocks into the clumps, compressing them to high densities. The clumps lose mass on relatively short timescales. The evolution of an individual clump is found to be sensitive to three dimensionless parameters: Nc0, the ratio of the initial column density of the clump to the column N(0) approx. 10(exp 21) cm(exp -2) of a warm FUV-heated surface region; upsilon, the ratio of the sound speed in the heated surface to that in the cold clump material: and t(FUV)t(c), the ratio of the "turn-on time" t(FUV) of the heating flux on a clump to its initial sound crossing-time t(c). The evolution also depends on whether a confining interclump medium exists, or whether the interclump region has negligible pressure, as is the case for turbulence-generated clumps. In this paper, we use spherical 1-D numerical hydrodynamic models as well as approximate analytical models to study the dependence of clump photoevaporation on the physical parameters of the clump, and to derive the dynamical evolution, mass loss rates and photoevaporative timescales of a clump for a variety of astrophysical situations. Turbulent clumps evolve so that their column densities are equal to a critical value determined by the local FUV field, and typically have short photo evaporation timescales, approx. 10(exp 4-5) years for a 1 M(solar mass) clump in a typical star-forming region (Nc0 = 10, upsilon = 10). Clumps with insufficient magnetic pressure support, and in strong FUV fields may be driven to collapse by the compressional effect of converging shock waves. We also estimate the rocket effect on photoevaporating clumps and find that it is significant only for the smallest clumps, with sizes much less than the extent of the PDR itself. Clumps that are confined by all interclump medium may either get completely photoevaporated, or may preserve a shielded core with a warm, dissociated, protective shell that, absorbs the incident FUV flux. We compare our results with observations of some well studied PDRs: the Orion Bar, M17SW NGC 2023 and the Rosette Nebula. The data are consistent with both interpretations of clump origin. turbulence and pressure confinement, with a slight indication for favouring the turbulent model for clumps over pressure-confined

Gorti, Uma↗
DOE OSTI2022

Photodissociation dynamics of xylene isomers C 6 H 4 (CH 3 ) 2 at 157nm using an ultracompact velocity map imaging spectrometer – The C 7 H 7 channel

Here, we investigated the photodissociation dynamics of three xylene isomers C 6 H 4 (CH 3 ) 2 at 157nm. The center-of-mass translational energy distributions of C 7 H 7 radicals were found to peak at 26kJmol −1 . Although the ionization energy of the C 7 H 7 tolyl fragment exceeds the energy of a 157nm photon, C 7 H 7 + was observed as a result of the photoionization of vibrationally ‘hot’ tolyl (C 7 H 7 ) radicals and/or two-photon ionization. The formation of rovibrationally excited tolyl fragments was discussed. Our experiments suggest the presence of tolyl radicals in the interstellar medium as a precursor to methylated polycyclic aromatic hydrocarbons upon reaction with vinylacetylene (C 4 H 4 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photodissociation and Theory to Investigate Uranium Oxide Cluster Cations

Uranium oxide cluster cations of the form U n O m + are produced by laser vaporization of a depleted uranium rod in a pulsed supersonic expansion. Ions are mass-analyzed and mass-selected with a time-of-flight spectrometer and studied with UV laser multiphoton dissociation. Cations of the stoichiometry UO 2 (UO 3 ) n + were observed as photofragments from all photodissociated cluster cations. (UO 3 ) n + clusters were also observed to result from dissociation of larger (UO 3 ) n + clusters, with UO 3 neutral as a common leaving group. Electronic structure calculations were used to investigate the stability of the prominent uranium oxide cluster cations using density functional theory (DFT) with the hybrid B3LYP exchange-correlation functional and at the CCSD(T) level and cc-pVnZ-PP basis sets (n = D,T), including diffuse orbitals as computational expense and availability permitted. Clustering energies, relative energies and dissociation energies of the cations are reported. The lowest energy neutral (UO 3 ) n clusters up to n = 3 are rings, n = 4 and 5 are chains with very low energy rings, and n = 6 is 3D. Finally, the lowest energy structures for UO 2 (UO 3 ) n + are composed of uranyl-like UO 2 + units bound by bridging oxygens to other UO 2 2+ units for n = 2 and 3, and for n = 4 a more complex 3D structure is predicted.

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

Photodissociation Dynamics of the Cyclohexyl Radical from the 3p Rydberg State at 248 nm

The photodissociation of jet-cooled cyclohexyl was studied by exciting the radicals to their 3p Rydberg state by using 248 nm laser light and detecting photoproducts by photofragment translational spectroscopy. Both H atom loss and dissociation to heavy fragment pairs are observed. The H atom loss channel exhibits a two-component translational energy distribution. The fast photoproduct component is attributed to impulsive cleavage directly from an excited state, likely the Rydberg 3s state, forming cyclohexene. The slow component is due to statistical decomposition of hot cyclohexyl radicals that internally convert to the ground electronic state prior to H atom loss. The fast and slow components are present in an ~0.7:1 ratio, similar to findings in other alkyl radicals. Internal conversion to the ground state also leads to ring-opening followed by dissociation to 1-buten-4-yl + ethene in comparable yield to H-loss, with the C 4 H 7 fragment containing enough internal energy to dissociate further to butadiene via H atom loss. A very minor ground-state C 5 H 8 + CH 3 channel is observed, attributed predominantly to 1,3-pentadiene formation. Lastly, the ground-state branching ratios agree well with RRKM calculations, which also predict C 4 H 6 + C 2 H 5 and C 3 H 6 + C 3 H 5 channels with similar yield to C 5 H 8 + CH 3 . If these channels were active, it was at levels too low to be observed.

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

Photodissociation Dynamics of CH 2 OO on Multiple Potential Energy Surfaces: Experiment and Theory

UV excitation of the CH 2 OO Criegee intermediate across most of the broad span of the (B 1A') – (X 1A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O ( 1 D) + H 2 CO (X 1 A 1 ) and O ( 3 P) + H 2 CO (a 3A"). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy (TKER) distribution for the O ( 1 D) + H 2 CO (X 1 A 1 ) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (E avl ), respectively. The unexpected low TKER component corresponds to highly internally excited H 2 CO (X 1 A 1 ) products accommodating ca. 80% of E avl . Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O ( 1 D) + H 2 CO (X 1 A 1 ) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H 2 CO (X 1 A 1 ) products. The remaining trajectories (11%) dissociate to O ( 3 P) + H 2 CO (a 3 A") products after traversing through both CoIn regions. Here, the complementary experimental and theoretical investigation provides insight on the photodissociation of CH 2 OO via multiple dissociation pathways through two regions of CoIn that control the branching and energy distributions of products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electron–Ion Covariance Reveals Geometry-Resolved Inner-Shell Spectra in CS 2 Photodissociation

The chemical shifts of inner-shell atomic orbitals are highly sensitive to chemical bonding and molecular structure. In evolving systems, however, the spectra of distinct molecular species and geometries overlap, obscuring the underlying chemical dynamics. Here we demonstrate the use of electron–ion covariance analysis to combine the structural sensitivity of Coulomb explosion imaging with inner-shell spectroscopy, yielding geometry-specific spectra of transient and product species. We apply this approach to the excited state dynamics of CS 2 probed by ionization above the S 2p edge. Electron–ion covariance with time- and momentum-selected S + and S 2+ ions isolates distinct S 2p photoelectron spectra for ground-state CS 2 , bent photoexcited CS 2 , the CS photoproduct, and bare atomic sulfur ─ species whose spectra overlap strongly in the channel-averaged measurement. Clear chemical shifts are observed in the covariance photoelectron spectrum for each of these species, all of which are consistent with high-level calculations. Here, by extracting the atomic S contribution to the photoelectron spectrum in a finely time-resolved manner we can disentangle this contribution to the overall time-resolved photoelectron spectrum as the photodissociation proceeds. These results demonstrate the promise of electron–ion covariance as a general approach to geometry-resolved inner-shell spectroscopy, opening a route to tracking structural evolution through chemical shifts in complex photoexcited molecules.

Ionization↗
DOE OSTI2022

Plasmon-Assisted Direct Interfacial Charge Transfer Enables Molecular Photodissociation on Metal Surfaces

Plasmonic photocatalysis is promising for driving reactions out of equilibrium, leading to enhanced rates and selectivity, but the energy and charge transfer mechanism at the interface remains to be explored. Here, we revisit visible-light plasmon-assisted photodissociation of dimethyl disulfide molecules (S–S bond cleavage) over single-crystalline silver and copper surfaces, using density functional theory calculations and the delta self-consistent field method. We investigate different excitation mechanisms and show that the direct intramolecular excitations, as suggested earlier to explain the experimental findings, cannot address the observed catalytic bond activation. Instead, the calculated excitations mediated by the metal Fermi level agree well with the threshold energy and maximum-yield energy in experiments and suggest that the reaction follows a direct interfacial charge transfer mechanism. Furthermore, we show that the excitation energy and the charge transfer can be modulated by introducing excess charges in the systems. Here, this study thus provides a fundamental understanding of interfacial charge transfer for driving plasmonic photocatalysis.

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

Ultrafast Production of NiCO and Ni Following 197 nm Photodissociation of Nickel Tetracarbonyl

Herein, we report on the ultrafast photodissociation of nickel tetracarbonyl—a prototypical metal–ligand model system—at 197 nm. Using mid-infrared transient absorption spectroscopy to probe the bound C≡O stretching modes, we find evidence for the picosecond time scale production of highly vibronically excited nickel dicarbonyl and nickel monocarbonyl, in marked contrast with a prior investigation at 193 nm. Further spectral evolution with a 50 ps time constant suggests an additional dissociation step; the absence of any corresponding growth in signal strongly indicates the production of bare Ni, a heretofore unreported product from single-photon excitation of nickel tetracarbonyl. Thus, by probing the deep UV-induced photodynamics of a prototypical metal carbonyl, this Letter adds time-resolved spectroscopic signatures of these dynamics to the sparse literature at high excitation energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗