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We have investigated the mid-infrared spectral characteristics of a series of polycyclic aromatic hydrocarbons (PAHs) with straight edges and containing an even or odd number of carbons using density functional theory (DFT). For several even and odd-carbon PAHs, the 8.6/6.2 and 7.6/6.2 intensity ratios computed in emission after the absorption of a 8 eV photon match the observed ratios obtained for three reflection nebulae (RNe), namely NGC 1333, NGC 7023, and NGC 2023. Odd-carbon PAHs are favored, particularly for NGC 1333. Both cations and anions are present with the cations being predominant. Relevant PAHs span sizes ranging from 46 to 103-113 carbons for NGC 7023 and NGC 2023 and from 38 to 127 carbons for NGC 1333 and have symmetries ranging from D2h to C s . Our work suggests that even and odd-carbon PAHs with straight edges are viable candidates for the PAH emission seen towards irradiated Photo-Dissociation Regions (PDRs).

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., Comment: accepted by ApJ

We present the first mid-infrared spectra of SMP LMC 11 in the Large Magellanic Cloud. While this object resembles a planetary nebula in the optical, its infrared properties are more similar to an object in transition from the asymptotic giant branch to the planetary nebula phase. A warm dust continuum dominates the infrared spectrum. The peak emission corresponds to a mean dust temperature of 330 K. The spectrum shows overlapping molecular absorption bands from 12 to 17 um corresponding to acetylene and polyacetylenic chains and benzene. This is the first detection of C4H2, C6H2, C6H6 and other molecules in an extragalactic object. The infrared spectrum of SMP LMC 11 is similar in many ways to that of the pre-planetary nebula AFGL 618. The IRS spectrum shows little evidence of nitrogen-based molecules which are commonly seen in Galactic AGB stars. Polycyclic aromatic hydrocarbons are also absent from the spectrum. The detection of the [NeII] 12.8 um line in the infrared and other forbidden emission lines in the optical indicates that an ionized region is present., 5 pages (in emulateapj), 1 table, 2 figures. Accepted for publication in ApJ Letters

Observations from the Spitzer Space Telescope have drawn attention to spectroscopic structure longward of 15 μm that is associated with objects showing prominent unidentified infrared (UIR) bands in the mid-IR. If polycyclic aromatic hydrocarbons (PAHs) are indeed responsible for the UIR features, longer wavelength emission arising from out-of-plane PAH skeletal vibrations is required. Here we compare some of the Spitzer spectra with spectra from the Infrared Space Observatory and analyze these data in terms of the PAH model utilizing the spectra of neutral PAHs from the Ames PAH IR spectral database. The 14-21 μm emission spectra from the H II region S106, the young stellar object CD -42°11721, the reflection nebula NGC 7023, and the H2 ridge in LkHα 234 are presented. We show that while the emission in this region can be quite variable, the bulk of these variations can be accommodated by variations in PAH population.

Infrared (IR) emission features at 3.3, 6.2, 7.7, 8.6, and 11.3 mum are generally attributed to IR fluorescence from ( mainly) far-ultraviolet (FUV) pumped large polycyclic aromatic hydrocarbon (PAH) molecules. As such, these features trace the FUV stellar flux and are thus a measure of star formation. We examined the IR spectral characteristics of Galactic massive star-forming regions and of normal and starburst galaxies, as well as active galactic nuclei (AGNs) and ultraluminous infrared galaxies (ULIRGs). The goal of this study is to analyze whether PAH features are a good qualitative and/or quantitative tracer of star formation, and hence to evaluate the application of PAH emission as a diagnostic tool in order to identify the dominant processes contributing to the infrared emission from Seyfert galaxies and ULIRGs. We develop a new mid-infrared (MIR)/far-infrared ( FIR) diagnostic diagram based on our Galactic sample and compare it to the diagnostic tools of Genzel and coworkers and Laurent and coworkers, with these diagnostic tools also applied to our Galactic sample. This MIR/FIR diagnostic is derived from the FIR normalized 6.2 mum PAH flux and the FIR normalized 6.2 mum continuum flux. Within this diagram, the Galactic sources form a sequence spanning a range of 3 orders of magnitude in these ratios, ranging from embedded compact H II regions to exposed photodissociation regions (PDRs) and the ( diffuse) interstellar medium ( ISM). However, the variation in the 6.2 mum PAH feature - to - continuum ratio is relative small. Comparison of our extragalactic sample with our Galactic sources revealed an excellent resemblance of normal and starburst galaxies to exposed PDRs. While Seyfert 2 galaxies coincide with the starburst trend, Seyfert 1 galaxies are displaced by at least a factor of 10 in 6.2 mum continuum flux, in accordance with general orientation-dependent unification schemes for AGNs. ULIRGs show a diverse spectral appearance. Some show a typical AGN hot dust continuum. More, however, either are starburst-like or show signs of strong dust obscuration in the nucleus. One characteristic of the ULIRGs also seems to be the presence of more prominent FIR emission than either starburst galaxies or AGNs. We discuss the observed variation in the Galactic sample in view of the evolutionary state and the PAH/dust abundance and discuss the use of PAHs as quantitative tracers of star formation activity. Based on these investigations, we find that PAHs may be better suited as a tracer of B stars, which dominate the Galactic stellar energy budget, than as a tracer of massive star formation (O stars).

We present spectra of the 3.3 mum and 11.2 mum polycyclic aromatic hydrocarbon (PAH) features of a large number of stellar sources, planetary nebulae, reflection nebulae, H II regions, and galaxies, obtained with Infrared Space Observatory Short Wavelength Spectrometer. Clear variations are present in the profiles of these features. Most of the sources show a symmetric 3.3 mum feature peaking at similar to3.290 mum, while only very few show an asymmetric 3.3 mum feature peaking at a slightly longer wavelength. The profiles of the 11.2 mum feature are distinctly asymmetric. The majority of the sources has a 11.2 mum feature peaking between 11.20 and 11.24 mum, with a very steep blue rise and a low tail-to-top ratio. A few sources show a 11.2 mum feature with a peak position of similar to11.25 mum, a less steep blue rise, and a high tail-to-top ratio. The sources are classified independently on the basis of the 3.3 and 11.2 mum feature profiles and peak positions. Correlations between these classes and those based on the 6-9 mum features (Peeters et al.) are found. In particular, sources with the most common profiles in the 6-9 mum region also show the most common 3.3 and 11.2 mum feature profiles. However, the uncommon profiles do not correlate with each other. Also, these classifications depend on the type of object. In general, H II regions, nonisolated Herbig AeBe stars and young stellar objects show the same profiles for all 3-12 mum features. Many planetary nebulae and post-asymptotic giant branch stars show uncommon feature profiles. The three galaxies in our sample show the same profiles as the H II regions for all but the 11.2 mum feature, being similar to that of evolved stars. The observed pronounced contrast in the spectral variations for the CH modes (3.3 and 11.2 mum bands) versus the CC modes (6.2, 7.7, and 8.6 mum bands) is striking: the peak wavelengths of the features attributed to CC modes vary by similar to15-80 cm(-1), while for the CH modes the variations are similar to4-6.5 cm(-1). We summarize existing laboratory data and theoretical calculations of the modes emitting in the 3-12 mum region of PAH molecules and complexes. In contrast to the 6.2 and 7.7 mum components, which are attributed to PAH cations, the 3.3 mum feature appears to originate in neutral and/or negatively charged PAHs. We attribute the variations in peak position and profile of these IR emission features to the composition of the PAH family. The variations in FWHM of the 3.3 mum feature remains an enigma, while those of the 11.2 mum can be explained by anharmonicity and molecular structure. The possible origin of the observed contrast in profile variations between the CH modes and the CC modes is highlighted.

We report infrared spectral evidence of deuterated interstellar polycyclic aromatic hydrocarbons (PAHs). Two bands are detected in the infrared emission from the ionization bar in Orion at 4.4 and 4.65 � m. The one at 4.65 � m is present at the 4.4 � level, while the one at 4.4 � m is more tentative, with aequal to 1.9. An emission band at 4.65 � m is also detected in the infrared emission from M17 by Verstraete and coworkers at the 4.4 � level. These wavelengths are highly characteristic of C-D stretching modes of deuterated PAHs and fall in a featureless region oftheinterstellarspectrum.TheIRspectroscopicpropertiesofdeuteratedPAHsaresummarized,andanestimateof the deuterium fractionation between the aromatic and aliphatic carbons associated with the PAHs is given. High deuterium fractionation is implied; this is discussed in terms of interstellar PAH fractionation mechanisms. Subject headings: astrochemistry — infrared: ISM — ISM: abundances — ISM: molecules — line: identification — techniques: spectroscopic

We present the first detection of unidentified infrared (UIR) emission features at ~6.4 and 7.9 μm in the spectrum of the dusty WC8 Wolf-Rayet star WR 48a. Based on the H-deficient nature of WC stars, we attribute the emission features to large carbonaceous molecules or amorphous carbon dust grains in the circumstellar environment of WR 48a. The 6.4 μm feature resembles the emission feature seen toward H-deficient planetary nebulae (PNe), while the 7.9 μm profile resembles that of some PNe with H-deficient WC10 central stars. These similarities point toward a similar origin of the dust in these H-deficient environments and highlights the apparent sensitivity of the UIR bands to physical conditions. In the case of WR 48a and the [WC10] PNe, shock processing may play a major role in dust formation.

We report new correlations between ratios of band intensities of the 15-20 {\mu}m emission bands of polycyclic aromatic hydrocarbons (PAHs) in a sample of fifty-seven sources observed with Spitzer/IRS. This sample includes Large Magellanic Cloud point sources from the SAGE-Spec survey, nearby galaxies from the SINGS survey, two Galactic ISM cirrus sources and the spectral maps of the Galactic reflection nebulae NGC 2023 and NGC 7023. We find that the 16.4, 17.4 and 17.8 {\mu}m band intensities are inter-correlated in all environments. In NGC 2023 and NGC 7023 these bands also correlate with the 11.0 and 12.7 {\mu}m band intensities. The 15.8 {\mu}m band correlates only with the 15-20 {\mu}m plateau and the 11.2 {\mu}m emission. We examine the spatial morphology of these bands and introduce radial cuts. We find that these bands can be spatially organized into three sets: the 12.7, 16.4 and 17.8 {\mu}m bands; the 11.2, 15.8 {\mu}m bands and the 15-18 {\mu}m plateau; and the 11.0 and 17.4 {\mu}m bands. We also find that the spatial distribution of the 12.7, 16.4 and 17.8 {\mu}m bands can be reconstructed by averaging the spatial distributions of the cationic 11.0 {\mu}m and neutral 11.2 {\mu}m bands. We conclude that the 17.4 {\mu}m band is dominated by cations, the 15.8 {\mu}m band by neutral species, and the 12.7, 16.4 and 17.8 {\mu}m bands by a combination of the two. These results highlight the importance of PAH ionization for spatially differentiating sub-populations by their 15-20 {\mu}m emission variability., Comment: 17 pages, 14 figures, Accepted for publication in ApJ

We present the results of a computational study to investigate the infrared spectroscopic properties of a large number of polycyclic aromatic hydrocarbon (PAH) molecules and their fully dehydrogenated counterparts. We constructed a database of fully optimized geometries for PAHs that is complete for eight or fewer fused benzene rings, thus containing 1550 PAHs and 805 fully dehydrogenated aromatics. A large fraction of the species in our database have clearly non-planar or curved geometries. For each species, we determined the frequencies and intensities of their normal modes using density functional theory calculations. Whereas most PAH spectra are fairly similar, the spectra of fully dehydrogenated aromatics are much more diverse. Nevertheless, these fully dehydrogenated species show characteristic emission features at 5.2??m, 5.5??m, and 10.6??m; at longer wavelengths, there is a forest of emission features in the 16-30??m range that appears as a structured continuum, but with a clear peak centered around 19??m. We searched for these features in Spitzer-IRS spectra of various positions in the reflection nebula NGC?7023. We find a weak emission feature at 10.68??m in all positions except that closest to the central star. We also find evidence for a weak 19??m feature at all positions that is not likely due to C60. We interpret these features as tentative evidence for the presence of a small population of fully dehydrogenated PAHs, and discuss our results in the framework of PAH photolysis and the formation of fullerenes.

Infrared spectra of carbon-rich objects which have evolved off the asymptotic giant branch reveal a range of dust properties, including fullerenes, polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and several unidentified features, including the 21 um emission feature. To test for the presence of fullerenes, we used the position and width of the feature at 18.7-18.9 um and examined other features at 17.4 and 6-9 um. This method adds three new fullerene sources to the known sample, but it also calls into question three previous identifications. We confirm that the strong 11 um features seen in some sources arise primarily from SiC, which may exist as a coating around carbonaceous cores and result from photo-processing. Spectra showing the 21 um feature usually show the newly defined Class D PAH profile at 7-9 um. These spectra exhibit unusual PAH profiles at 11-14 um, with weak contributions at 12.7 um, which we define as Class D1, or show features shifted to ~11.4, 12.4, and 13.2 um, which we define as Class D2. Alkyne hydrocarbons match the 15.8 um feature associated with 21 um emission. Sources showing fullerene emission but no PAHs have blue colors in the optical, suggesting a clear line of sight to the central source. Spectra with 21 um features and Class D2 PAH emission also show photometric evidence for a relatively clear line of sight to the central source. The multiple associations of the 21 um feature to aliphatic hydrocarbons suggest that the carrier is related to this material in some way., 30 pages, 30 figures, ApJ, in press

As a result of an error at the Publisher, problems occurred in the presentation of Figures 4, 7, and 8. Figure 4 was printed without the mid-IR spectral data for the CH out-of-plane bending vibrations. The figure is printed here in its entirety. The example portions of online Figure sets 7 and 8 were presented in print in a low-resolution format. Similarly, the figure sets were presented online in low resolution and each part of the set was presented separately. The example portions of these figure sets are presented below as intended, and the online sets for Figures 7 and 8 are available online in higher resolution, arranged in a grid. IOP Publishing sincerely regrets these errors.

We present 15-20 um spectral maps towards the reflection nebula NGC2023 obtained with the Infrared Spectrograph in short-wavelength, high-resolution mode on board the Spitzer Space Telescope. These spectra reveal emission from PAHs, C60, and H2 superposed on a dust continuum. These emission components exhibit distinct spatial distributions: with increasing distance from the illuminating star, we observe the PAH emission followed by the dust continuum emission and the H2 emission. The C60 emission is located closest to the illuminating star in the south while in the north, it seems to be associated with the H/H2 transition. Emission from PAHs and PAH-related species produce features at 15.8, 16.4, 17.4, and 17.8 um and the 15-18 um plateau. These different PAH features show distinct spatial distributions. The 15.8 um band and 15-18 um plateau correlate with the 11.2 um PAH band and with each other, and are attributed to large, neutral PAHs. Conversely, the 16.4 um feature correlates with the 12.7 um PAH band, suggesting that both arise from species that are favored by the same conditions that favor PAH cations. The PAH contribution to the 17.4 um band is displaced towards the illuminating star with respect to the 11.2 and 12.7 um emission and is assigned to doubly ionized PAHs and/or a subset of cationic PAHs. The spatial distribution of the 17.8 um band suggests it arises from both neutral and cationic PAHs. In contrast to their intensities, the profiles of the PAH bands and the 15-18 um plateau do not vary spatially. Consequently, we conclude that the carrier of the 15-18 um plateau is distinct from that of the PAH bands., 34 pages, 8 fig. To appear in ApJ (accepted)

The far-IR characteristics of astrophysically relevant polycyclic aromatic hydrocarbons (PAHs) averaging in size around 100 carbon atoms have been studied using the theoretical spectra in the NASA Ames PAH IR Spectroscopic Database. These spectra were calculated using density functional theory. Selections of PAH species are made, grouped together by common characteristics or trends, such as size, shape, charge, and composition, and their far-IR spectra compared. The out-of-plane modes involving the entire molecule are explored in detail, astronomical relevance is assessed, and an observing strategy is discussed. It is shown that PAHs produce richer far-IR spectra with increasing size. PAHs also produce richer far-IR spectra with increasing number of irregularities. However, series of irregular-shaped PAHs with the same compact core have common "Jumping-Jack" modes that "pile up" at specific frequencies in their average spectrum. For the PAHs studied here, around 100 carbon atoms in size, this band falls near 50 μm. PAH charge and nitrogen inclusion affect band intensities but have little effect on far-IR band positions. Detailed analysis of the two-dimensional, out-of-plane bending "drumhead" modes in the coronene and pyrene "families" and the one-dimensional, out-of-plane bending "bar" modes in the acene "family" show that these molecular vibrations can be treated as classical vibrating sheets and bars of graphene, respectively. The analysis also shows that the peak position of these modes is very sensitive to the area of the emitting PAH and does not depend on the particular geometry. Thus, these longest wavelength PAH bands could provide a unique handle on the size of the largest species in the interstellar PAH family. However, these bands are weak. Observing highly excited regions showing the mid-IR bands in which the emission from classical dust peaks at short wavelengths offers the best chance of detecting PAH emission in the far-IR. For these regions sensitivity is not an issue, spectral contrast is maximized and the PAH population is only comprised of highly stable, compact symmetric PAHs, such as the members of the pyrene and coronene "families" discussed in detail here.