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Barker, J. R.

Publications and source records attributed to Barker, J. R..

15 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

Atmospheric Chemistry↗
NASA NTRS2009

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 16. Supplement to Evaluation 15: Update of Key Reactions

This is the supplement to the fifteenth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available in electronic form and may be printed from the following Internet URL: http://jpldataeval.jpl.nasa.gov/.

atmospheric modeling↗
NASA NTRS1989

Interstellar polycyclic aromatic hydrocarbons - The infrared emission bands, the excitation/emission mechanism, and the astrophysical implications

A comprehensive study of the PAH hypothesis is presented, including the interstellar, IR spectral features which have been attributed to emission from highly vibrationally excited PAHs. Spectroscopic and IR emission features are discussed in detail. A method for calculating the IR fluorescence spectrum from a vibrationally excited molecule is described. Analysis of interstellar spectrum suggests that the PAHs which dominate the IR spectra contain between 20 and 40 C atoms. The results are compared with results from a thermal approximation. It is found that, for high levels of vibrational excitation and emission from low-frequency modes, the two methods produce similar results. Also, consideration is given to the relationship between PAH molecules and amorphous C particles, the most likely interstellar PAH molecular structures, the spectroscopic structure produced by PAHs and PAH-related materials in the UV portion of the interstellar extinction curve, and the influence of PAH charge on the UV, visible, and IR regions.

Allamandola, L. J.↗
NASA NTRS1987

The IR emission features - Emission from PAH molecules and amorphous carbon particles

Techniques for the assessment of the importance of the various forms of PAHs, and recent infrared observations concerning the PAH problem, are considered. Spectroscopic data suggest that the observed interstellar spectrum is due to both free molecule-sized PAHs producing the narrow features, and amorphous carbon particles contributing to the broad underlying components. Explanations for the multicomponent emission spectrum are discussed. A model of the emission mechanism for the example of chrysene is presented, and an exact treatment of the IR fluorescence from highly vibrationally excited large molecules shows that species containing 20-30 carbon atoms are responsible for the narrow features, although the spectra more closely resemble those of amorphous carbon particles. It is suggested that future emphasis should be placed on the spatial characteristics of the component spectra.

Allamandola, L. J.↗
NASA NTRS1987

The IR emission features - Emission from PAH molecules and amorphous carbon particles

Given the current understanding of polycyclic aromatic hydrocarbons (PAHs), the spectroscopic data suggest that are at least two components which contribute to the interstellar emission spectrum: (1) free molecule-sized PAHs producing the narrow features and (2) amorphous carbon particles (which are primarily composed of an irregular 'lattice' of PAHs) contributing to the broad underlying components. An exact treatment of the IR fluorescence from highly vibrationally excited large molecules demonstrates that species containing between 20 and 30 carbon atoms are responsible for the narrow features, although the spectra match more closely with the spectra of amorphous carbon particles. It is concluded that, since little is known about the spectroscopic properties of free PAHs and PAH clusters, much laboratory work is required along with an observational program focusing on the spatial characteristics of the spectra.

Allamandola, L. J.↗
NASA NTRS1987

The hydrogen coverage of interstellar PAHs

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a UV photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense UV fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments.

Tielens, A. G. G. M.↗
NASA NTRS1987

Infrared absorption and emission characteristics of interstellar PAHs

The mid-infrared interstellar emission spectrum with features at 3.28, 6.2, 7.7, 8.7 and 11.3 microns is discussed in terms of the Polycyclic Aromatic Hydrocarbon (PAH) hypothesis, which is based on the suggestive, but inconclusive comparison between the interstellar emission spectrum with the infrared absorption and Raman spectra of a few PAHs. The fundamental vibrations of PAHs and PAH-like species which determine the IR and Raman properties are discussed. Interstellar IR band emission is due to relaxation from highly vibrationally excited PAHs excited by ultraviolet photons. The excitation/emission process is described and the IR fluorescence from one PAH, chrysene, is traced. Generally, there is sufficient energy to populate several vibrational levels in each mode. Molecular vibrational potentials are anharmonic and emission from these higher levels will fall at lower frequencies and produce weak features to the red of the stronger fundamentals. This process is also described and can account for some spectroscopic details of the interstellar emission spectra previously unexplained. Analysis of the interstellar spectrum shows that PAHs contain between 20 and 30 carbon atoms and are responsible for the emission.

Allamandola, L. J.↗
NASA NTRS1987

Infrared emission from interstellar PAHs

The mid-IR absorption and Raman spectra of polycyclic aromatic hydrocarbons (PAHs) and the mechanisms determining them are reviewed, and the implications for observations of similar emission spectra in interstellar clouds are considered. Topics addressed include the relationship between PAHs and amorphous C, the vibrational spectroscopy of PAHs, the molecular emission process, molecular anharmonicity, and the vibrational quasi-continuum. Extensive graphs, diagrams, and sample spectra are provided, and the interstellar emission bands are attributed to PAHs with 20-30 C atoms on the basis of the observed 3.3/3.4-micron intensity ratios.

Allamandola, L. J.↗
NASA NTRS1986

The hydrogen coverage of interstellar PAHs

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a UV photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense UV fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments.

Barker, J. R.↗
NASA NTRS1986

Infrared absorption and emission characteristics of interstellar PAHs

The mid-infrared interstellar emission spectrum with features at 3.28, 6.2, 7.7, 8.7 and 11.3 microns is discussed in terms of the Polycyclic Aromatic Hydrocarbon (PAH) hypothesis, which is based on the suggestive, but inconclusive comparison between the interstellar emission spectrum with the infrared absorption and Raman spectra of a few PAHs. The fundamental vibrations of PAHs and PAH-like species which determine the IR and Raman properties are discussed. Interstellar IR band emission is due to relaxation from highly vibrationally excited PAHs excited by ultraviolet photons. The excitation/emission process is described and the IR fluorescence from one PAH, chrysene, is traced. Generally, there is sufficient energy to populate several vibrational levels in each mode. Molecular vibrational potentials are anharmonic and emission from these higher levels will fall at lower frequencies and produce weak features to the red of the stronger fundamentals. This process is also described and can account for some spectroscopic details of the interstellar emission spectra previously unexplained. Analysis of the interstellar spectrum shows that PAHs contain between 20 and 30 carbon atoms are responsible for the emission.

Barker, J. R.↗
NASA NTRS1986

N2O5 photolysis products investigated by fluorescence and optoacoustic techniques

Pulsed laser photolysis of N2O5 near 290 nm, coupled with fluorescence detection (calibrated by NO2 photoloysis), showed that the O(P-3) quantum yield is not more than 0.1. A pulsed laser optoacoustic technique in a flow tube was tested by photolysis of NO2 and then applied to N2O5. Nitric oxide was added to react with NO3 free radicals; the resulting increase in the optoacoustic signal confirmed the presence of NO3 free radicals. Based on the relative optoacoustic signals observed for NO2 and N2O5, the quantum yield for NO3 production is 0.8 + or - 0.2.

Barker, J. R.↗
NASA NTRS1985

Polycyclic aromatic hydrocarbons and the unidentified infrared emission bands - Auto exhaust along the Milky Way

The unidentified infrared emission features (UIR bands) are attributed to a collection of partially hydrogenated, positively charged polycyclic aromatic hydrocarbons (PAHs). This assignment is based on a spectroscopic analysis of the UIR bands. Comparison of the observed interstellar 6.2 and 7.7-micron bands with the laboratory measured Raman spectrum of a collection of carbon-based particulates (auto exhaust) shows a very good agreement, supporting this identification. The infrared emission is due to relaxation from highly vibrationally and electronically excited states. The excitation is probably caused by UV photon absorption. The infrared fluorescence of one particular, highly vibrationally excited PAH (chrysene) is modeled. In this analysis the species is treated as a molecule rather than bulk material and the non-thermodynamic equilibrium nature of the emission is fully taken into account. From a comparison of the observed ratio of the 3.3 to 11.3-micron UIR bands with the model calculations, the average number of carbon atoms per molecule is estimated to be about 20. The abundance of interstellar PAHs is calculated to be about 2 x 10 to the -7th with respect to hydrogen.

Allamandola, L. J.↗
NASA NTRS1983

Homogeneous processes of atmospheric interest

Upper atmospheric research programs in the department of chemical kinetics are reported. Topics discussed include: (1) third-order rate constants of atmospheric importance; (2) a computational study of the HO2 + HO2 and DO2 + DO2 reactions; (3) measurement and estimation of rate constants for modeling reactive systems; (4) kinetics and thermodynamics of ion-molecule association reactions; (5) entropy barriers in ion-molecule reactions; (6) reaction rate constant for OH + HOONO2 yields products over the temperature range 246 to 324 K; (7) very low-pressure photolysis of tert-bytyl nitrite at 248 nm; (8) summary of preliminary data for the photolysis of C1ONO2 and N2O5 at 285 nm; and (9) heterogeneous reaction of N2O5 and H2O.

Rossi, M. J.↗
NASA NTRS1979

Reaction rate and products for the reaction O/3P/ + H2CO

A study of reaction kinetics of O + H2CO in a discharge-flow system using mass spectrometric detection of reactants and products is presented. It was performed under both oxygen-atom-rich and formaldehyde-rich conditions over the 296 to 437 K range, showing that the global bimolecular rate constant is in agreement with other studies. This study differs from others in that the reaction products can be observed, and a substantial yield of a primary reaction product was measured with a mass spectral peak at m/e=44. This suggests that the global reaction rate probably consists of combination, as well as of simple abstraction. For the combination, one hypothesis is that triplet dioxymethylene is formed which polymerizes to triplet formic acid; the vibrationally excited triplet formic acid may decompose to form several sets of products, including HCO + OH and HCO2 + H.

Chang, J. S.↗