Large PAHs Research Articles

PAH and Dust Processing in Supernova Remnants

I present observations of shock-processed PAHs and dust in supernova remnants (SNRs). Supernova shocks are one of the primary sites destroying, fragmenting and altering interstellar PAHs and dust. Studies of PAHs through supernova shocks had been limited because of confusion with PAHs in background emission. Spitzer observations with high sensitivity and resolution allow us to separate PAHs associated with the SNRs and unrelated, Galactic PAHs. In the young SNR N132D, PAH features are detected with a higher PAH ratio of 15–20/7.7 μ m than those of other astronomical objects, and we suggest large PAHs have survived behind the shock. We present the spectra of additional 14 SNRs observed with Spitzer IRS and MIPS SED covering the range of 5–90 μ m. Bright PAH features from 6.2 to 15–20 μ m are detected from many of SNRs which emit molecular hydrogen lines, indicating that both large and small PAHs survive in low velocity shocks. We observe a strong correlation between PAH detection and carbonaceous small grains, while a few SNRs with dominant silicate dust lack PAH features. We characterize PAHs depending on the shock velocity, preshock density and temperature of hot gas, and discuss PAH and dust processing in shocks and implication of PAH and dust cycles in ISM.

Interaction of atomic hydrogen with carbon grains

Laboratory studies on the interaction of atomic hydrogen with aliphatic and aromatic hydrogenated carbon grains are discussed. When exposed to atomic hydrogen, both types of hydrogenated carbon grains act as catalysts for molecular hydrogen formation. In the first case, an exchange reaction with hydrogen chemisorbed in aliphatic carbon sites is the formation route to H2 formation. For aromatic carbon grains, the formation of molecular hydrogen takes place through a two-step reaction sequence: 1) super hydrogenation of the aromatic carbon islands of grains 2) exchange reactions on these islands. This mechanism represents a good approximation of molecular hydrogen formation on large neutral PAHs.

The role of PAHs in the physics of the interstellar medium

In the interstellar medium (ISM), PAHs are abundant and also carry most of the dust surface. They are thus privileged sites for surface reactions such as the formation of H2. In regions penetrated by UV photons, PAHs loose electrons by the photoelectric effect and efficiently heat the gas. In more shielded regions, PAH recombine and may carry an important fraction of the cloud electronic charge which plays an important role in the gas dynamics and chemistry. We review here processes involving PAHs which control key aspects of the physics of the ISM. We also discuss the corresponding observational constraints. Most of these processes involve a detailed knowledge of the charge of PAHs and we therefore review current models in this area. We argue that more laboratory measurements of the rate of electronic capture on large PAH cations are needed.

UNUSUAL PAH EMISSION IN NEARBY EARLY-TYPE GALAXIES: A SIGNATURE OF AN INTERMEDIATE-AGE STELLAR POPULATION?

We present the analysis of Spitzer-IRS spectra of four early-type galaxies, NGC 1297, NGC 5044, NGC 6868, and NGC 7079, all classified as LINERs in the optical bands. Their IRS spectra present the full series of H2 rotational emission lines in the range 5--38 microns, atomic lines, and prominent PAH features. We investigate the nature and origin of the PAH emission, characterized by unusually low 6 -- 9/11.3 microns inter-band ratios. After the subtraction of a passive early type galaxy template, we find that the 7 -- 9 microns spectral region requires dust features not normally present in star forming galaxies. Each spectrum is then analyzed with the aim of identifying their components and origin. In contrast to normal star forming galaxies, where cationic PAH emission prevails, our 6--14 microns spectra seem to be dominated by large and neutral PAH emission, responsible for the low 6 -- 9/11.3 microns ratios, plus two broad dust emission features peaking at 8.2 microns and 12 microns. Theses broad components, observed until now mainly in evolved carbon stars and usually attributed to pristine material, contribute approximately 30-50% of the total PAH flux in the 6--14 microns region. We propose that the PAH molecules in our ETGs arise from fresh carbonaceous material which is continuously released by a population of carbon stars, formed in a rejuvenation episode which occurred within the last few Gyr. The analysis of the MIR spectra allows us to infer that, in order to maintain the peculiar size and charge distributions biased to large and neutral PAHs, this material must be shocked, and excited by the weak UV interstellar radiation field of our ETG.

Electronic absorption spectroscopy of polycyclic aromatic hydrocarbons (PAHs) radical cations generated in oleum: A superacid medium

Oleum (fuming sulphuric acid), a well known superacid, was used as medium for the generation of the radical cation of a series of selected PAHs. The resulting radical cation spectra were studied by electronic absorption spectroscopy. Not only common PAHs like naphthalene, anthracene, tetracene, pentacene, perylene, pyrene, benzo[ a]pyrene, phenanthrene and picene were studied but also the less common and very large PAHs relevant also for the astrochemical research, like coronene, hexabenzocoronene, quaterrylene, dicoronylene and a coronene oligomer. A correlation between the first ionization potential ( I P1) of the PAHs studied and the energy to the so-called A-type band of the radical cations observed in oleum has led to the equation I P1 = 1.30 E A + 4.39 (in eV) which permits to estimate the energy of the PAHs radical cation transition ( E A) in the VIS-NIR knowing the relative ionization potential or vice versa.

Observations and modeling of the dust emission from the H2-bright galaxy-wide shock in Stephan's Quintet

Spitzer Space Telescope observations revealed powerful mid-infrared (mid-IR) H2 rotational line emission from the Stephan's Quintet (SQ) X-ray emitting large scale shock associated with a collision between two galaxies. Because H2 forms on dust grains, the presence of H2 is physically linked to the survival of dust, and we expect some dust emission to come from the molecular gas. To test this interpretation, IR observations and dust modeling are used to identify and characterize the thermal dust emission from the shocked molecular gas. The spatial distribution of the IR emission allows us to isolate the faint PAH and dust continuum emission associated with the molecular gas in the SQ shock. We model the spectral energy distribution (SED) of this emission, and fit it to Spitzer observations. Faint PAH and dust continuum emission are detected in the SQ shock, outside star-forming regions. The 12/24um flux ratio in the shock is remarkably close to that of the diffuse Galactic interstellar medium, leading to a Galactic PAH/VSG abundance ratio. However, the properties of the PAH emission spectrum in the shock differ from that of the Galaxy, which may suggest an enhanced fraction of large and neutrals PAHs. The IR SED is consistent with the expected emission from dust associated with the warm (>150K) H2 gas, heated by a UV radiation field of intensity comparable to that of the solar neighborhood, in agreement with GALEX UV observations. The presence of PAHs and dust grains in the high-speed (1000km/s) galaxy collision suggests that dust survives. We propose that the dust that survived destruction was in pre-shock gas at densites larger than a few 0.1cm-3, which was not shocked at velocities larger than 200km/s. [abridged]

Where is the warm H2? A search for H2emission from disks around Herbig Ae/Be stars

Mid-IR emission lines of H2 are useful probes to determine the mass of warm gas present in the surface layers of disks. Numerous observations of Herbig Ae/Be stars (HAeBes) have been performed, but only 2 detections of mid-IR H2 toward HD97048 and AB Aur have been reported. We aim at tracing the warm gas in the disks of 5 HAeBes with gas-rich environments and physical characteristics close to those of AB Aur and HD97048, to discuss whether the detections toward these 2 objects are suggestive of peculiar conditions for the gas. We search for the H2 S(1) emission line at 17.035 \mu\m with VISIR, and complemented by CH molecule observations with UVES. We gather the H2 measurements from the literature to put the new results in context and search for a correlation with some disk properties. None of the 5 VISIR targets shows evidence for H2 emission. From the 3sigma upper limits on the integrated line fluxes we constrain the amount of optically thin warm gas to be less than 1.4 M_Jup in the disk surface layers. There are now 20 HAeBes observed with VISIR and TEXES instruments to search for warm H2, but only two detections (HD97048 and AB Aur) were made so far. We find that the two stars with detected warm H2 show at the same time high 30/13 \mu\m flux ratios and large PAH line fluxes at 8.6 and 11.3 \mu\m compared to the bulk of observed HAeBes and have emission CO lines detected at 4.7 \mu\m. We detect the CH 4300.3A absorption line toward both HD97048 and AB Aur with UVES. The CH to H2 abundance ratios that this would imply if it were to arise from the same component as well as the radial velocity of the CH lines both suggest that CH arises from a surrounding envelope, while the detected H2 would reside in the disk. The two detections of the S(1) line in the disks of HD97048 and AB Aur suggest either peculiar physical conditions or a particular stage of evolution.

ANOMALOUS SILICATE DUST EMISSION IN THE TYPE 1 LINER NUCLEUS OF M81

We report the detection and successful modeling of the unusual 9.7\mum Si--O stretching silicate emission feature in the type 1 (i.e. face-on) LINER nucleus of M81. Using the Infrared Spectrograph (IRS) instrument on Spitzer, we determine the feature in the central 230 pc of M81 to be in strong emission, with a peak at ~10.5\mum. This feature is strikingly different in character from the absorption feature of the galactic interstellar medium, and from the silicate absorption or weak emission features typical of galaxies with active star formation. We successfully model the high signal-to-noise ratio IRS spectra with porous silicate dust using laboratory-acquired mineral spectra. We find that the most probable fit uses micron-sized, porous grains of amorphous silicate and graphite. In addition to silicate dust, there is weak PAH emission present (particularly at 11.3\mum, arising from the C--H out-of-plane bending vibration of relatively large PAHs of ~500--1000 C atoms) whose character reflects the low-excitation AGN environment, with some evidence that small PAHs of ~100--200 C atoms (responsible for the 7.7\mum C--C stretching band) in the immediate vicinity of the nucleus have been preferentially destroyed. (abstract continues)

Polycyclic aromatic hydrocarbon processing in interstellar shocks

Context: PAHs appear to be an ubiquitous interstellar dust component but the effects of shocks waves upon them have never been fully investigated. Aims: To study the effects of energetic (~0.01-1 keV) ion (H, He and C) and electron collisions on PAHs in interstellar shock waves.Methods: We calculate the ion-PAH and electron-PAH nuclear and electronic interactions, above the threshold for carbon atom loss from a PAH, in 50-200 km/s shock waves in the warm intercloud medium. Results: Interstellar PAHs (Nc = 50) do not survive in shocks with velocities greater than 100 km/s and larger PAHs (Nc = 200) are destroyed for shocks with velocities greater/equal to 125 km/s. For shocks in the ~75 - 100 km/s range, where destruction is not complete, the PAH structure is likely to be severely denatured by the loss of an important fraction (20-40%) of the carbon atoms. We derive typical PAH lifetimes of the order of a few x10^8 yr for the Galaxy. These results are robust and independent of the uncertainties in some key parameters that have yet to be well-determined experimentally. Conclusions: The observation of PAH emission in shock regions implies that that emission either arises outside the shocked region or that those regions entrain denser clumps that, unless they are completely ablated and eroded in the shocked gas, allow dust and PAHs to survive in extreme environments.

Large polycyclic aromatic hydrocarbons: Synthesis and discotic organization

Abstract Polycyclic aromatic hydrocarbons (PAHs) have attracted enormous interest due to their unique electronic and optoelectronic properties as well as the potential applications in organic electronics. This article reviews the progress in the modern synthesis of large PAHs with different sizes, shapes, edge structures, and substituents. Due to their outstanding self-organization characteristics, the discotic liquid-crystalline properties, self-assembled nanostructures on the surfaces, as well as the application in electronic devices will be discussed.

THE INFRARED SPECTRA OF VERY LARGE IRREGULAR POLYCYCLIC AROMATIC HYDROCARBONS (PAHs): OBSERVATIONAL PROBES OF ASTRONOMICAL PAH GEOMETRY, SIZE, AND CHARGE

The mid-IR spectra of six large, irregular PAHs with formulae (C84H24 - C120H36) have been computed using Density Functional Theory (DFT). Trends in the dominant band positions and intensities are compared to those of large, compact PAHs as a function of geometry, size and charge. Irregular edge moieties that are common in terrestrial PAHs, such as bay regions and rings with quartet hydrogens, are shown to be uncommon in astronomical PAHs. As for all PAHs comprised solely of C and H reported to date, mid-IR emission from irregular PAHs fails to produce a strong CCstr band at 6.2 um, the position characteristic of the important, class A astronomical PAH spectra. Earlier studies showed inclusion of nitrogen within a PAH shifts this to 6.2 um for PAH cations. Here we show this band shifts to 6.3 um in nitrogenated PAH anions, close to the position of the CC stretch in class B astronomical PAH spectra. Thus nitrogenated PAHs may be important in all sources and the peak position of the CC stretch near 6.2 um appears to directly reflect the PAH cation to anion ratio. Large irregular PAHs exhibit features at 7.8 um but lack them near 8.6 um. Hence, the 7.7 um astronomical feature is produced by a mixture of small and large PAHs while the 8.6 um band can only be produced by large compact PAHs. As with the CCstr, the position and profile of these bands reflect the PAH cation to anion ratio.

A statistical approach to develop a detailed soot growth model using PAH characteristics

A detailed PAH growth model is developed, which is solved using a kinetic Monte Carlo algorithm. The model describes the structure and growth of planar PAH molecules, and is referred to as the kinetic Monte Carlo–aromatic site (KMC-ARS) model. A detailed PAH growth mechanism based on reactions at radical sites available in the literature, and additional reactions obtained from quantum chemistry calculations are used to model the PAH growth processes. New rates for the reactions involved in the cyclodehydrogenation process for the formation of 6-member rings on PAHs are calculated in this work based on density functional theory simulations. The KMC-ARS model is validated by comparing experimentally observed ensembles on PAHs with the computed ensembles for a C 2H 2 and a C 6H 6 flame at different heights above the burner. The motivation for this model is the development of a detailed soot particle population balance model which describes the evolution of an ensemble of soot particles based on their PAH structure. However, at present incorporating such a detailed model into a population balance is computationally unfeasible. Therefore, a simpler model referred to as the site-counting model has been developed, which replaces the structural information of the PAH molecules by their functional groups augmented with statistical closure expressions. This closure is obtained from the KMC-ARS model, which is used to develop correlations and statistics in different flame environments which describe such PAH structural information. These correlations and statistics are implemented in the site-counting model, and results from the site-counting model and the KMC-ARS model are in good agreement. Additionally the effect of steric hindrance in large PAH structures is investigated and correlations for sites unavailable for reaction are presented.

High-resolution infrared absorption spectroscopy of thermally excited naphthalene. Measurements and calculations of anharmonic parameters and vibrational interactions

We report in this paper the recording and analysis of the vibrational spectrum of naphthalene in the 1.6-200 microm (50-6000 cm(-1)) spectral range with a resolution of 0.005 cm(-1). The spectrum, recorded at room temperature, shows several complex structures in the Q branches of the c-type bands, which can be assigned to hot-band sequences as well as combination bands and overtones. To analyse the experimental data, we developed a model based on anharmonic calculations which predicts the transitions (positions and intensities) involving the vibrational levels populated at room temperature. This work permits us to estimate the validity and limitations of our calculations, which can be used to predict the band profiles of naphthalene (and larger PAHs) at various temperatures, with potential astrophysical applications.

Modeling the interstellar aromatic infrared bands with co-added spectra of PAHs

The observed variations in profiles of the interstellar aromatic infrared bands correlate with the object type and are indicative of PAH populations existing i n different sources. Spectroscopic studies on PAHs can provide tools for the int erpretation of variations accompanying the AIBs. As the observed spectra results from a mix of possible species in the region attempt is made to model this comp osite spectra by co-adding emissions from PAHs in different size groups. Theoretical IR data of PAHs having 10 to 96 carbon atoms is used to obtain emis sion spectra. The models are taken in size groups making up of small, medium and large PAHs. The models show good profile match with observations for the 7.7 $\mu m$ complex having sub-features at 7.6 and 7.8 $\mu m$. The 7.6 $\mu m$ sub-feature dominates in the spectra of medium sized PAH cations matching observations from UV rich interstellar environments. The 7.8 $\mu m$ component is more intense in the spectra of large PAH cations (model III) correlating with observations from benign astrophysical regions. A possible interpretation for the observations of $C-H$ out-of-plane bend modes and the weak outliers on the blue side of the intense 11.2 $\mu m$ band is proposed. The models provide pointers to possible PAH populations in different regions.

Large PAHs detected in fine particulate matter emitted from light-duty gasoline vehicles

Emission factors of large PAHs with 6–8 aromatic rings with molecular weights (MW) of 300–374 were measured from 16 light-duty gasoline-powered vehicles (LDGV) and one heavy-duty diesel-powered vehicle (HDDV) operated under realistic driving conditions. LDGVs emitted PAH isomers of MW 302, 326, 350, and 374, while the HDDV did not emit these compounds. This suggests that large PAHs may be useful tracers for the source apportionment of gasoline-powered motor vehicle exhaust in the atmosphere. Emission rates of MW 302, 326, and 350 isomers from LDGVs equipped with three-way catalysts (TWCs) ranged from 2 to 10 (μg L −1 fuel burned), while emissions from LDGVs classified as low emission vehicles (LEVs) were almost a factor of 10 lower. MW 374 PAH isomers were not quantified due to the lack of a quantification-grade standard. The reduced emissions associated with the LEVs are likely attributable to improved vapor recovery during the “cold-start” phase of the Federal Test Procedure (FTP) driving cycle before the catalyst reaches operating temperature. Approximately 2 (μg g −1 PM) of MW 326 and 350 PAH isomer groups were found in the National Institute of Standards and Technology standard reference material (SRM)#1649 (Urban Dust). The pattern of the MW 302, 326, and 350 isomers detected in SRM#1649 qualitatively matched the ratio of these compounds detected in the exhaust of TWC LDGVs suggesting that each gram of Urban Dust SRM contained 5–10 mg of PM originally emitted from gasoline-powered motor vehicles. Large PAHs made up 24% of the total LEV PAH emissions and 39% of the TWC PAH emissions released from gasoline-powered motor vehicles. Recent studies have shown certain large PAH isomers have greater toxicity than benzo[ a]pyrene. Even though the specific toxicity measurements on PAHs with MW >302 have yet to be performed, the detection of significant amounts of MW 326 and 350 PAHs in motor vehicle exhaust in the current study suggests that these compounds may pose a significant public health risk.

Theoretical infrared spectra of large polycyclic aromatic hydrocarbons

Theoretical and experimental spectroscopic studies have underlined the contribution of large PAHs towards the astrophysical mid-infrared emission bands. Quantum chemical study of eight large PAHs using density functional theory approach is reported along with their infrared spectra. Systematic variation of bands with PAH size is noted and a better agreement with the observed astrophysical bands is obtained. Compared to small and medium sized PAHs there is substantial C–H stretch intensity in the cation spectra. This is attributed to smaller change in charge on the hydrogens upon ionization. For the C–H out-of-plane mode large PAHs correlate well with observed features on the shorter wavelength side of the 11.2 μ m band. Presence of two sub-components of the broad 7.7 μ m band in large PAHs compares very well with the corresponding astrophysical band and point to the abundance of large PAH cations in interstellar environments. The data presented here may be used for a more detailed study on the profile variations accompanying the mid-IR bands in various interstellar environments.

From branched hydrocarbon propellers to C3-symmetric graphite disks.

Branched hydrocarbon propellers (9 and 12) were prepared by stepwise palladium-catalyzed Hagihara-Sonogashira coupling reactions and Diels-Alder cycloadditions and submitted to oxidative cyclodehydrogenation by FeCl3 to afford two new giant graphite disks 2 and 3 with 3-fold symmetry in high yield. One of the precursors, the polyphenylene dendrimer 9 containing 150 carbon atoms, was crystallographically characterized. The poorly soluble graphite disks were characterized by isotope-resolved MALDI-TOF mass spectroscopy, and their electronic and vibrational properties were investigated by solid-state UV-vis and Raman spectroscopy. The effect of molecular size and geometry on their properties was discussed. The molecule 2 represents the largest, 3-fold-symmetric all-benzenoid graphite disk, and the five-membered rings in molecule 3 open the opportunity to synthesize large bowl-shaped PAHs.

Combined UV-biological degradation of PAHs

The UV-photolysis of PAHs was tested in silicone oil and tetradecane. In most cases, the degradation of a pollutant provided within a mixture was lower than when provided alone due to competitive effects. With the exception of anthracene, the larger pollutants (4- and 5-rings) were always degraded first, proving that UV-treatment preferentially acts on large PAHs and thereby provides a good complement to microbial degradation. UV-photolysis was also found to be suitable for treatment of soil extract from contaminated soils. The feasibility of UV-biological treatment was demonstrated for the removal of a mixture of phenanthrene and pyrene in silicone oil. UV-irradiation of the silicone oil led to 83% pyrene removal but no phenanthrene photodegradation. Subsequent treatment of the oil in a two-phases partitioning bioreactor (TPPB) system inoculated with Pseudomonas sp. was followed by complete phenanthrene biodegradation but no further pyrene removal. Totally, the combined process allowed 92% removal of the PAH mixture. Further work should focus on characterizing the photoproducts formed and studying the influence of the solvent on the photodegradation process.

Recovery of semivolatile organic compounds during sample preparation: implications for characterization of airborne particulate matter.

Semivolatile compounds present special analytical challenges not met by conventional methods for analysis of ambient particulate matter (PM). Accurate quantification of PM-associated organic compounds requires validation of the laboratory procedures for recovery over a wide volatility and polarity range. To meet these challenges, solutions of n-alkanes (nC12-nC40) and polycyclic aromatic hydrocarbons PAHs (naphthalene to benzo[ghi]perylene) were reduced in volume from a solvent mixture (equal volumes of hexane, dichloromethane and methanol), to examine recovery after reduction in volume. When the extract solution volume reached 0.5 mL the solvent was entirely methanol, and the recovery averaged 60% for n-alkanes nC12-nC25 and PAHs from naphthalene to chrysene. Recovery of higher MW compounds decreased with MW, because of their insolubility in methanol. When the walls of the flasks were washed with 1 mL of equal parts hexane and dichloromethane (to reconstruct the original solvent composition), the recovery of nC18 and higher MW compounds increased dramatically, up to 100% for nC22-nC32 and then slowly decreasing with MW due to insolubility. To examine recovery during extraction of the components of the High Capacity Integrated Gas and Particle Sampler, the same standards were used to spike its denuders and filters. For XAD-4 coated denuders and filters, normalized recovery was >95% after two extractions. Recovery from spiked quartz filters matched the recovery from the coated surfaces for alkanes nC18 and larger and for fluoranthene and larger PAHs. Lower MW compounds evaporated from the quartz filter with the spiking solvent. This careful approach allowed quantification of organics by correcting for volatility- and solubility-related sample preparation losses. This method is illustrated for an ambient sample collected with this sampler during the Texas Air Quality Study 2000.

Reassessment of the Hydrocarbons in Prince William Sound and the Gulf of Alaska: Identifying the Source Using Partial Least-Squares

There has been considerable exchange in the literature regarding the source of the background hydrocarbons in Prince William Sound and the Gulf of Alaska. Page and coworkers suggest oil-based sources while Short and coworkers suggest coal. The multivariate statistical methodology of partial least-squares (PLS) has been used to reassess the percentage contribution of coal, seep oil, shales, and rivers to the hydrocarbon loading in the Gulf of Alaska. Data have kindly been provided by Short (NOAA) and Page (Bowdoin College, for Exxon), and these have been analyzed using selected sites as sources in order to develop signatures. These signatures are based on 40 and 136 compounds, respectively, and include the PAH and terpane/sterane biomarkers in the case of the Exxon data. The principal components describing these sources are then fitted to the data for other sites around the Prince William Sound (PWS) and Gulf of Alaska (GoA) to determine the proportion of the variability described by each source. Using the Exxon data, a mixed source of coal, seep oil, eroding shales, and rivers (1 and 2) sources described approximately 13%, 18%, 24%, 26%, and 20%, respectively, of the variance in PWS and GoA data. The rivers 1 signature was very similar to that of coal, while rivers 2 was more similar to the eroding shales. New coal data (Short, unpublished work) also indicated considerable overlap with the Exxon seep oil. With the NOAA data, spatial plots of the explained variance indicate that the prespill background has a wide range of explained fits. There is considerable overlap in the signatures developed from the data, and Coomans' Plots identify those compounds which are the most diagnostic: for the Exxon seep oil signature, naphthalene and methyl- and dimethylnaphthalene are the best markers, whereas for the NOAA prespill background, Exxon coals and shales are best defined by the larger PAHs such as benzo[ghi]perylene. The evidence suggests mixed sources whose contributions vary significantly across the sampling area.