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All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Origins of interstellar and solar system: Carbonaceous materials

Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.

Feigelson, Eric D.↗
NASA NTRS1996

Assessment of the polycyclic aromatic hydrocarbon-diffuse interstellar band proposal

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high-energy range of the spectrum, and possesses a large oscillator strength), and seems to correlate with strong and broad DIBs. For noncompact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low-energy range of the spectrum, and possesses a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that (i) only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narow bands on the other can easily be interpreted in the context of the PAH proposal by a distribution of compact and noncompact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would reflect conditions within a cloud which locally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations in the ultraviolet range, is called for.

NASA Discipline Number 52-10↗
NASA NTRS1995

Assessment of the Polycyclic Aromatic Hydrocarbon-Diffuse Interstellar Band Proposal

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high energy range of the spectrum, and possess a large oscillator strength), and seems to correlate with strong and broad DIBs. In the case of non-compact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low energy range of the spectrum, and possess a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that: (i) Only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narrow bands on the other hand can easily be interpreted in the context of the PAH proposal by a distribution between compact and non-compact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would provide tracers of conditions within a cloud which globally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations of the ultraviolet range, is called for.

Salama, Farid↗
NASA NTRS1994

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

NASA Discipline Exobiology↗
NASA NTRS1999

Tholins: Can They Provide a Substrate, Carbon and Nitrogen for Plant Production?

Tholin is a word coined to describe the entire class of complex organic solids produced in laboratory experiments where pre-biotic gaseous chemicals are subject to bombardment by high energy. The atomic composition of Titan tholin produced from 10 percent CH4 and 90 percent N2 in a simulation of Titan atmosphere irradiated by charged particles trapped in the magnetosphere of Saturn gave 67 percent C and 33 percent N. Hydrolysis of Titan tholin with 6N HCl produced a racemic mixture of biological and non-biological amino acids that was confirmed by GC/MS. Other tholins, that revealed the presence of amino acids, were UV tholin produced under possible primitive Earth conditions by irradiation of a mixture of gases (CH4, C2H6, NH3, H2S and liquid H2O) with long-wavelength ultraviolet light, representing the most abundant useful energy source for prebiological organic synthesis; Spark tholin in a crude simulation of Jupiter atmosphere using electrical discharge through a mixture of CH4, NH3, and H2O vapor. Pyrolytic GC/MS of Titan tholin produced more than one hundred organic compounds including saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. Similar rich pyrolytic products were obtained with UV as well as Spark tholins. A range of two to four ring PAHs (Polycyclic Aromatic Hydrocarbons) in Spark as well as Titan tholins, some with one to four alkylation sites, were identified by two-step laser desorption/multiphoton ionization mass spectrometry and also confirmed by the synchronous fluorescence technique. Previous studies have demonstrated the potential for use of tholins as a source of carbon and energy by microbes. This paper describes studies that evaluate the potential for using different types of tholins as (a) a substrate for growing plants and (b) a source of carbon and nitrogen for plants. The data are interpreted in terms of the potential for using such tholins to grow plants for food in extraterrestrial habitats and also to speculate on the possibilities of abiotic evolution of plants.

Wignarajah, Kanapathipillai↗
DOE OSTI2024

Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.

Kinetic Modeling↗
NASA NTRS2011

Atmospheric Chemistry of Micrometeoritic Organic Compounds

Micrometeorites approx.100 m in diameter deliver most of the Earth s annual accumulation of extraterrestrial material. These small particles are so strongly heated upon atmospheric entry that most of their volatile content is vaporized. Here we present preliminary results from two sets of experiments to investigate the fate of the organic fraction of micrometeorites. In the first set of experiments, 300 m particles of a CM carbonaceous chondrite were subject to flash pyrolysis, simulating atmospheric entry. In addition to CO and CO2, many organic compounds were released, including functionalized benzenes, hydrocarbons, and small polycyclic aromatic hydrocarbons. In the second set of experiments, we subjected two of these compounds to conditions that simulate the heterogeneous chemistry of Earth s upper atmosphere. We find evidence that meteor-derived compounds can follow reaction pathways leading to the formation of more complex organic compounds.

Kress, M. E.↗
NASA NTRS2017

The Detection of 6.9 µm Emission Features in the Infrared Spectra of IRAS 04296+3429, IRAS 05341+0852, IRAS 22272+5435: Evidence for the Presence of Hn-PAHs in Post AGB Stars

Polycyclic aromatic hydrocarbons (PAHs) are generally believed to be ubiquitous in space and responsible for numerous telltale interstellar infrared emission bands. In Sandford et al., (2013), we suggested that polycyclic aromatic hydrocarbons with excess hydrogenation at their periphery (Hn-PAHs) may be an important subclass of these molecules in some astrophysical environments. These molecules are candidates to explain objects with anomalously large 3.4 μm features, which are presumed to be associated with the aliphatic C—H stretching vibrations of the excess hydrogen. In that work, we suggest that for Hn-PAHs to be a viable candidate as the source for this 3.4 μm feature, we must also expect to observe methylene scissoring modes at 6.9 μm. In this work, we continue to develop the Hn-PAH hypothesis with a focus on the 6.9 μm feature. We also present some new observations of three post-asymptotic giant branch (post- AGB) objects with abnormally large 3.4 μm features, IRAS 04296+3429, IRAS 05341+0852, IRAS 22272+5435, in addition to one post-AGB object with normal PAH emissions, IRAS 20000+3239. These observations were made using the FORCAST instrument in grism mode on the Stratospheric Observatory for Infrared Astronomy (SOFIA) aircraft (Adams et al. 2010) and demonstrate the presence of a 6.9 μm feature for the three objects with abnormally large 3.4 μm features and no detectable 6.9 μm feature for the normal PAH emitter. These results are consistent with the hypothesis that Hn-PAHs are a possible source of these infrared emission bands.

ISM↗
NASA NTRS2002

Website for the Astrochemistry Laboratory, Astrophysics Branch, Space Sciences Division

The Astrochemistry Laboratory in the Astrophysics Branch (SSA) of the Space Sciences Division at NASA's Ames Research Center specializes in the study of extraterrestrial materials and their analogs. The staff has pioneered laboratory studies of space environments including interstellar, cometary, and planetary ices, simulations of the so-called 'Unidentified' Infrared Emission Bands and Diffuse Interstellar Bands using PAHs (Polycyclic Aromatic Hydrocarbons) and PAH-related materials, and has extensive experience with low-temperature spectroscopy and astronomical observation. Important discoveries made by the Astrochemistry Group include: (1) The recognition that polycyclic aromatic hydrocarbons and their ions are common in space; (2) The identification of a major fraction of the known molecular species frozen in interstellar/pre-cometary ices; (3) The recognition that a significant fraction of the carbon in the interstellar medium is carried by both microdiamonds and organic materials; (4) The expansion of the types of molecules expected to be synthesized in interstellar/pre-cometary ices. These could be delivered to the early Earth (or other body) and influence the origin or early evolution of life.

Sandford, Scott↗
NASA NTRS2002

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

Mattioda, A. L.↗
NASA NTRS1977

Compounds in airborne particulates - Salts and hydrocarbons

Concentrations of 10 polycyclic aromatic hydrocarbons (PAH), the aliphatics as a group, sulfate, nitrate, fluoride, acidity, and carbon in the airborne particulate matter were measured at 16 sites in Cleveland, OH over a 1-year period during 1971 and 1972. Analytical methods used included gas chromatography, colorimetry, and combustion techniques. Uncertainties in the concentrations associated with the sampling procedures, and the analytical methods are evaluated. The data are discussed relative to other studies and source origins. High concentrations downwind of coke ovens for 3,4 benzopyrene are discussed. Hydrocarbon correlation studies indicated no significant relations among compounds studied.

King, R. B.↗
DOE OSTI2024

Aryl hydrocarbon receptor-dependent toxicity by retene requires metabolic competence

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds frequently detected in the environment with widely varying toxicities. Many PAHs activate the aryl hydrocarbon receptor (AHR), inducing the expression of a battery of genes, including xenobiotic metabolizing enzymes like cytochrome P450s (CYPs); however, not all PAHs act via this mechanism. We screened several parent and substituted PAHs in in vitro AHR activation assays to classify their unique activity. Retene (1-methyl-7-isopropylphenanthrene) displays Ahr2-dependent teratogenicity in zebrafish, but did not activate human AHR or zebrafish Ahr2, suggesting a retene metabolite activates Ahr2 in zebrafish to induce developmental toxicity. To investigate the role of metabolism in retene toxicity, studies were performed to determine the functional role of cyp1a, cyp1b1, and the microbiome in retene toxicity, identify the zebrafish window of susceptibility, and measure retene uptake, loss, and metabolite formation in vivo. Cyp1a-null fish were generated using CRISPR-Cas9. Cyp1a-null fish showed increased sensitivity to retene toxicity, whereas Cyp1b1-null fish were less susceptible, and microbiome elimination had no significant effect. Zebrafish required exposure to retene between 24 and 48 hours post fertilization (hpf) to exhibit toxicity. After static exposure, retene concentrations in zebrafish embryos increased until 24 hpf, peaked between 24 and 36 hpf, and decreased rapidly thereafter. We detected retene metabolites at 36 and 48 hpf, indicating metabolic onset preceding toxicity. This study highlights the value of combining molecular and systems biology approaches with mechanistic and predictive toxicology to interrogate the role of biotransformation in AHR-dependent toxicity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Iraq/Afghanistan war lung injury reflects burn pits exposure

This descriptive case series retrospectively reviewed medical records from thirty-one previously healthy, war-fighting veterans who self-reported exposure to airborne hazards while serving in Iraq and Afghanistan between 2003 and the present. They all noted new-onset dyspnea, which began during deployment or as a military contractor. Twenty-one subjects underwent non-invasive pulmonary diagnostic testing, including maximum expiratory pressure (MEP) and impulse oscillometry (IOS). In addition, five soldiers received a lung biopsy; tissue results were compared to a previously published sample from a soldier in our Iraq Afghanistan War Lung Injury database and others in our database with similar exposures, including burn pits. We also reviewed civilian control samples (5) from the Stony Brook University database. Military personnel were referred to our International Center of Excellence in Deployment Health and Medical Geosciences, Donald and Barbara Zucker School of Medicine at Hofstra/Northwell under the auspices of Northwell IRB: 17-0140-FIMR Feinstein Institution for Medical Research “Clinicopathologic characteristics of Iraq Afghanistan War Lung Injury.” We retrospectively examined medical records, including exposure data, radiologic imaging, and non-invasive pulmonary function testing (MGC Diagnostic Platinum Elite Plethysmograph) using the American Thoracic Society (ATS) standard interpretation based on Morgan et al., and for a limited cohort, biopsy data. Lung tissue, when available, was examined for carbonaceous particles, polycyclic aromatic hydrocarbons (Raman spectroscopy), metals, titanium connected to iron (Brookhaven National Laboratory, National Synchrotron Light Source II, Beamline 5-ID), oxidized metals, combustion temperature, inflammatory cell accumulation and fibrosis, neutrophil extracellular traps, Sirius red, Prussian Blue, as well as polarizable crystals/particulate matter/dust. Among twenty-one previously healthy, deployable soldiers with non-invasive pulmonary diagnostic tests, post-deployment, all had severely decreased MEP values, averaging 42% predicted. These same patients concurrently demonstrated abnormal airways reactance (X5Hz) and peripheral/distal airways resistance (D5–D20%) via IOS, averaging – 1369% and 23% predicted, respectively. These tests support the concept of airways hyperresponsiveness and distal airways narrowing, respectively. Among the five soldiers biopsied, all had constrictive bronchiolitis. We detected the presence of polycyclic aromatic hydrocarbons (PAH)—which are products of incomplete combustion—in the lung tissue of all five warfighters. All also had detectable titanium and iron in the lungs. Metals were all oxidized, supporting the concept of inhaling burned metals. Combustion temperature was consistent with that of burned petrol rather than higher temperatures noted with cigarettes. All were nonsmokers. Neutrophil extracellular traps were reported in two biopsies. Compared to our prior biopsies in our Middle East deployment database, these histopathologic results are similar, since all database biopsies have constrictive bronchiolitis, one has lung fibrosis with titanium bound to iron in fixed mathematical ratios of 1:7 and demonstrated polarizable crystals. These results, particularly constrictive bronchiolitis and polarizable crystals, support the prior data of King et al. (N. Engl. J. Med. 365:222–230, 2011) Soldiers in this cohort deployed to Iraq and Afghanistan since 2003, with exposure to airborne hazards, including sandstorms, burn pits, and improvised explosive devices, are at high risk for developing chronic clinical respiratory problems, including: (1) reduction in respiratory muscle strength; (2) airways hyperresponsiveness; and (3) distal airway narrowing, which may be associated with histopathologic evidence of lung damage, reflecting inhalation of burned particles from burn pits along with particulate matter/dust. Non-invasive pulmonary diagnostic tests are a predictor of burn pit-induced lung injury

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

ICEE: Next Generation Exobiology and Astrobiology Studies

The presence of organic molecules, from simple to complex form are found in the ISM (interstellar medium). Perhaps the largest of these molecules are the PAHs, or polycyclic aromatic hydrocarbons, while smaller versions of PAHs have been identified in meteorites, IDPs (interplanetary dust particles) and comets within the Solar System. Life is comprised of organic molecules and, in one sense; the search for life is the search for and identification of organic molecules. This yields an interesting question. Can the organics in the ISM serve as the chemical feedstock to the prebiotic molecules identified in meteorites, comets and IDPs in a “Top-Down” synthesis mechanism? Most studies regarding the formation of prebiotic molecules focus on a “Bottoms-Up” mechanism, whereby simple organic compounds in ice form larger, more biologically relevant molecules when exposed to UV irradiation. Here we present a next generation experimental setup which focuses on if larger, interstellar organics, such as PAHs (polycyclic aromatic hydrocarbons) can serve as the chemical feedstock for the organic inventory found in the Solar System.

A. L. Mattioda↗
DOE OSTI2023

Radical–Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C 6 H 5 ) with propargyl radical (H 2 CCCH) provides an important prototype for radical–radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300–1000 K and pressure range of 4–10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C 9 H 8 and C 9 H 7 + H product channels and report experimental isomer-resolved product branching fractions for the C 9 H 8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. Here, these ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical–radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C 9 H 7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C 9 H 7 ) recombination to indene and H-assisted isomerization that converts less stable C 9 H 8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Gas-Phase Synthesis of Coronene through Stepwise Directed Ring Annulation

Molecular beam experiments together with electronic structure calculations provide the first evidence of a complex network of elementary gas-phase reactions culminating in the bottom-up preparation of the 24π aromatic coronene (C 24 H 12 ) molecule–a representative peri-fused polycyclic aromatic hydrocarbon (PAH) central to the complex chemistry of combustion systems and circumstellar envelopes of carbon stars. The gas-phase synthesis of coronene proceeds via aryl radical-mediated ring annulations through benzo[e]pyrene (C 20 H 12 ) and benzo[ghi]perylene (C 22 H 12 ) involving armchair-, zigzag-, and arm-zig-edged aromatic intermediates, highlighting the chemical diversity of molecular mass growth processes to polycyclic aromatic hydrocarbons. Furthermore, the isomer-selective identification of five- to six-ringed aromatics culminating with the detection of coronene is accomplished through photoionization and is based upon photoionization efficiency curves along with photoion mass-selected threshold photoelectron spectra, providing a versatile concept of molecular mass growth processes via aromatic and resonantly stabilized free radical intermediates to two-dimensional carbonaceous nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Red fluorescence and 3-12 micron emission in NGC 2023, HD 44179, M 82, and Lynds 1780

A red excess observed in the Red Rectangle (HD 44179), was attributed to a possible molecular fluorescence mechanism was discovered in NGC 2023 and analyzed in subsequent work in this and other nebulae. An unexpected red light excess was also noticed in a high latitude dark cloud L 1780. The fluorescence was attributed to hydrogenated amorphous carbon by Duley (1985), on the basis of laboratory work. Alternatively, transitions between electronic states of free polycyclic aromatic hydrocarbon molecules, by-passing the cascade along the vibrational states was considered. In L 1780, the red excess was related to the 12 micron emission detected by IRAS. A quantitative comparison of the intensity of the red fluorescence and that of the 3 to 12 micron features is thus warranted in helping assess the physical properties of large interstellar molecules. The red fluorescence radiation, F(R), appears as a bump on the spectra between 0.6 and 0.9 micron. Values were deduced from the spectra for HD 44179, and for the high latitude cloud L 1780. Corrections for the extinction, both interstellar and internal to the nebulae, were included. The 3 to 12 micron brightness, F(IR), was obtained through integration of the spectra for NGC 2023, and for HD 44179 after removal of a smooth continuum due to hot large grains. The values of the ratio of fluorescence flux to the infrared flux, F(R)/F(IR), are summarized. Red fluorescence and infrared radiation are two separate ways to access to the size of the molecules through observation, and it is rewarding that both approaches give similar results. These findings bring a striking coherence into the physical description of the particles, and add further support to the initial attribution of the infrared features to polycyclic aromatic hydrocarbons (PAHs).

Ryter, Charles↗
DOE OSTI2024

Hydrogen ejection from hydrocarbons: Characterization and relevance in soot formation and interstellar chemistry

Polycyclic aromatic hydrocarbons (PAHs) play a major role in the chemistry of combustion, pyrolysis, and the interstellar medium. Production (or activation) of radical PAHs and propagation of their resulting reactions require efficient dehydrogenation, but the preferred method of hydrogen loss is not well understood. Unimolecular hydrogen ejection (i.e., direct C─H bond fission) and bimolecular radical abstraction are two main candidate pathways. We performed a computational study to characterize the role of H ejection, particularly as a driver for radical-centric hydrocarbon-growth mechanisms and particle formation. Electronic structure calculations establish that C─H bond strengths span a broad range of energies, which can be weaker than 30 kcal/mol in some C 9 and C 13 PAH radicals. At T > 1200 K, calculated thermal rates for hydrogen ejection from weak C─H bonds at zigzag sites on PAH radicals are significantly larger than typical H-abstraction rates. These results are highly relevant in the context of chain reactions of radical species and soot inception under fuel-rich combustion conditions. Furthermore, calculated microcanonical rates that include the additional internal energy released by bond formation (e.g., ring closure to yield C 9 H 9 ) yield significantly higher rates than those associated with full thermalization. These microcanonical considerations are relevant to the astrochemical processes associated with hydrocarbon growth and processing in the low-density interstellar environment.

08 HYDROGEN↗