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[Abridged] JWST observations of the Orion Bar have shown the incredible richness of PAH bands and their variation on small scales. We aim to probe the photochemical evolution of PAHs across the key zones of the photodissociation region (PDR) that is the Orion Bar using unsupervised machine learning. We use NIRSpec and MIRI IFU data from the JWST ERS Program PDRs4All. We lever bisecting k-means clustering to generate detailed spatial maps of the spectral variability in several wavelength regions. We discuss the variations in the cluster profiles and connect them to the local physical conditions. We interpret these variations with respect to the key zones: the HII region, the atomic PDR zone, and the three dissociation fronts. The PAH emission exhibits spectral variation that depends strongly on spatial position in the PDR. We find the 8.6um band to behave differently than all other bands which vary systematically with one another. We find uniform variation in the 3.4-3.6um bands and 3.4/3.3 intensity ratio. We attribute the carrier of the 3.4-3.6um bands to a single side group attached to very similarly sized PAHs. Cluster profiles reveal a transition between characteristic profiles classes of the 11.2um feature from the atomic to the molecular PDR zone. We find the carriers of each of the profile classes to be independent, and reason the latter to be PAH clusters existing solely deep in the molecular PDR. Clustering also reveals a connection between the 11.2 and 6.2um bands; and that clusters generated from variation in the 10.9-11.63um region can be used to recover those in the 5.95-6.6um region. Clustering is a powerful tool for characterizing PAH variability on both spatial and spectral scales. For individual bands as well as global spectral behaviours, we find UV-processing to be the most important driver of the evolution of PAHs and their spectral signatures in the Orion Bar., Comment: 28 pages, 20 figures, submitted to A&A

A first look is taken at the NIRSpec 1-5 $\mu$m observations from JWST program 1591 that targets 7 objects along the low-mass stellar life cycle with PAH emission. Spectra extracted from a 1.5$^{\prime\prime}$ radius sized circular aperture are explored, showing a wealth of features, including the 3 $\mu$m PAH complex, the PAH-continuum, and atomic and molecular emission lines from HI, He, H$_{\rm 2}$, and other species. CO$_{\rm 2}$- and H$_{\rm 2}$O-ice absorption and CO emission is also seen. Focusing on the bright-PDR position in M17, the PAH CH stretch falls at 3.29 $\mu$m (FWHM=0.04 $\mu$m). Signs of its 1.68 $\mu$m overtone are confused by line emission in all targets. Multi-component decomposition reveals a possible aliphatic deuterated PAH feature centered at 4.65 $\mu$m (FWHM=0.02 $\mu$m), giving [D/H]$_{\rm alip.}$=31$\pm$12.7%. However, there is little sign of its aromatic counterpart between 4.36-4.43 $\mu$m. There is also little sign of PAH-nitrile emission between 4.34-4.39 $\mu$m. A PAH continuum rises from $\sim$1 to 3.2 $\mu$m, after which it jumps by about a factor of 2.5 at 3.6 $\mu$m, with bumps at 3.8, 4.04, and 4.34 $\mu$m adding structure. The CO$_{\rm 2}$ absorption band in M17 is matched with 10:1 H$_{\rm 2}$O:CO$_{\rm 2}$ ice at 10 K. The $v$=0 pure rotational molecular hydrogen population diagram reveals $>$2200 K UV-pumped gas. The hydrogen Pfund series runs from levels 10 to $>$30. Considering Br$\alpha$/Br$\beta$=0.381$\pm$0.01966 and Case B recombination results in A$_{\rm V}{\simeq}$8. CO emission in IRAS21282+5050 originates from 258 K gas. In-depth spectral-spatial analysis of all features and targets are planned for a series of forthcoming papers., Comment: 23 pages, 20 figures, to be published in ApJ

We examine the dependence of polycyclic aromatic hydrocarbon (PAH) band intensity ratios as a function of the average number of carbon atoms and assess their effectiveness as tracers for PAH size, utilising the data, models, and tools provided by the NASA Ames PAH Infrared Spectroscopic Database. To achieve this, we used spectra from mixtures of PAHs of different ionisation fractions, following a size distribution. Our work, congruent with earlier findings, shows that band ratios that include the 3.3 ${\mu}$m PAH band provide the best PAH size tracers for small-to-intermediate sized PAHs. In addition, we find that band ratios that include the sum of the 15-20 ${\mu}$m PAH features (I$_{\Sigma_{15-20}}$) and the 6.2 or 7.7 ${\mu}$m bands also serve as good tracers for PAH size in the case of small-to-intermediate sized PAHs, for objects under a similar PAH size distribution as with the presented models. For different PAH size distributions, the application of a scaling factor to the I$_{6.2}$/I$_{\Sigma_{15-20}}$ ratio can provide estimates for the size of the small-to-intermediate PAH population within sources. Employment of the I$_{6.2}$/I$_{\Sigma_{15-20}}$ and I$_{7.7}$/I$_{\Sigma_{15-20}}$ ratios can be of particular interest for JWST observations limited only to $\sim$ 5-28 ${\mu}$m MIRI(-MRS) coverage., Comment: 8 pages, 5 figures; Accepted for publication in MNRAS

Utilizing the data and tools provided through the NASA Ames PAH IR Spectroscopic Database (PAHdb), we study the PAH component of over 900 Spitzer-IRS galaxy spectra. Employing a database-fitting approach, the average PAH size, the PAH size distribution, and PAH ionization fraction are deduced. In turn, we examine their connection with the properties of the host galaxy. We found that PAH population within galaxies consists of middle-sized PAHs with an average number of carbon atoms of $\bar{N_{C}}$ = 55, and a charge state distribution of $\sim$40% ionized - 60% neutral. We describe a correlation between the 6.2/11.2 $\mu$m PAH ratio with the ionization parameter ($\gamma\equiv(G_{0}/n_{\rm e})(T_{\rm gas} / 1\ \mathrm{K})^{0.5}$), a moderate correlation between the 8.6/11.2 $\mu$m PAH ratio and specific star-formation rate, and a weak anti-correlation between $\gamma$ and M$_{*}$. From the PAHdb decomposition we provide estimates for the 3.3 $\mu$m PAH band, not covered by Spitzer observations, and establish a correlation between the 3.3/11.2 $\mu$m PAH ratio with N$_{\mathrm{C}}$. We further deliver a library of mid-IR PAH template spectra parameterized on PAH size and ionization fraction, which can be used in galaxy spectral energy distribution fitting codes for the modeling of the mid-IR PAH emission component in galaxies., Comment: 28 pages, 19 figures, 4 tables. Accepted for publication in ApJ

Massive stars disrupt their natal molecular cloud material through radiative and mechanical feedback processes. These processes have profound effects on the evolution of interstellar matter in our Galaxy and throughout the Universe, from the era of vigorous star formation at redshifts of 1-3 to the present day. The dominant feedback processes can be probed by observations of the Photo-Dissociation Regions (PDRs) where the far-ultraviolet photons of massive stars create warm regions of gas and dust in the neutral atomic and molecular gas. PDR emission provides a unique tool to study in detail the physical and chemical processes that are relevant for most of the mass in inter- and circumstellar media including diffuse clouds, proto-planetary disks and molecular cloud surfaces, globules, planetary nebulae, and star-forming regions. PDR emission dominates the infrared (IR) spectra of star-forming galaxies. Most of the Galactic and extragalactic observations obtained with the James Webb Space Telescope (JWST) will therefore arise in PDR emission. In this paper we present an Early Release Science program using the MIRI, NIRSpec, and NIRCam instruments dedicated to the observations of an emblematic and nearby PDR: the Orion Bar. These early JWST observations will provide template datasets designed to identify key PDR characteristics in JWST observations. These data will serve to benchmark PDR models and extend them into the JWST era. We also present the Science-Enabling products that we will provide to the community. These template datasets and Science-Enabling products will guide the preparation of future proposals on star-forming regions in our Galaxy and beyond and will facilitate data analysis and interpretation of forthcoming JWST observations., Comment: Submitted to PASP

The PAH model predicts many weak emission features in the 1-5 $\mu$m region that can resolve significant questions that it has faced since its inception in the mid-80s. These features contain fundamental information about the PAH population that is inaccessible via the much stronger PAH bands in the 5-20 $\mu$m region. Apart from the 3.3 $\mu$m band and plateau, PAH spectroscopy across most of the 1-5 $\mu$m region has been unexplored due to its low intrinsic intensity. ISO and Akari covered some of this wavelength range, but lacked the combined sensitivity and resolution to measure the predicted bands with sufficient fidelity. The spectroscopic capabilities of the NIRSpec instrument on board JWST will make it possible to measure and fully characterize many of the PAH features expected in this region. These include the fundamental, overtone and combination C-D and C$\equiv$N stretching bands of deuterated PAHs, cyano-PAHs (PAH-C$\equiv$ N), and the overtones and combinations of the strong PAH bands that dominate the 5-20 $\mu$m region. These bands will reveal the amount of D tied up in PAHs, the PAH D/H ratio, the D distribution between PAH aliphatic and aromatic subcomponents, and delineate key stages in PAH formation and evolution on an object-by-object basis and within extended objects. If cyano-PAHs are present, these bands will also reveal the amount of cyano groups tied up in PAHs, determine the N/C ratio within that PAH subset, and distinguish between the bands near 4.5 $\mu$m that arise from CD versus C$\equiv$N., Comment: 13 page, 5 figures, 2 tables

We present insights into the behavior of the astronomical 7.7 ${\mu}$m polycyclic aromatic hydrocarbon (PAH) emission complex as gleaned from analyzing synthesized spectra, utilizing the data and tools from the NASA Ames PAH IR Spectroscopic Database. We specifically study the influence of PAH size, charge, aliphatic content and nitrogen substitution on the profile and peak position of the 7.7 ${\mu}$m feature (${\lambda}$7.7). The 7.7 ${\mu}$m band is known to vary significantly from object-to-object in astronomical observations, but the origin of these variations remains highly speculative. Our results indicate that PAH size can accommodate the largest shift in ${\lambda}$7.7 (~0.4 ${\mu}$m), where relatively small PAHs are consistent with class A spectra (fewer than 60 carbon atoms) while large PAHs are consistent with red/very red class B spectra. Aliphatic PAHs, of which our sample only contains a few, can produce redshifts typically around 0.15 ${\mu}$m; changes in ionization fraction, depending on the species, produce shifts up to 0.1 ${\mu}$m; and nitrogen substitution has no effect on ${\lambda}$7.7. Within the limits of our study, the class B-to-A transition is best explained with a changing PAH size distribution, with a relatively minor role assigned to aliphatic content and varying charge states. The resulting astronomical picture is that the photochemical evolution of PAHs moving from shielded class C/B environments into exposed ISM-like class A environments may be intrinsically different from the reverse class A-to-B transition of interstellar PAHs being incorporated into newly-forming star systems., Comment: 21 pages, 12 figures; accepted for publication in The Astrophysical Journal

Photodissociation regions (PDRs) contain a large fraction of all of the interstellar matter in galaxies. Classical examples include the boundaries between ionized regions and molecular clouds in regions of massive star formation, marking the point where all of the photons energetic enough to ionize hydrogen have been absorbed. In this paper we determine the physical properties of the PDRs associated with the star forming regions IRAS 23133+6050 and S 106 and present them in the context of other Galactic PDRs associated with massive star forming regions. We employ Herschel PACS and SPIRE spectroscopic observations to construct a full 55-650 {\mu}m spectrum of each object from which we measure the PDR cooling lines, other fine- structure lines, CO lines and the total far-infrared flux. These measurements are then compared to standard PDR models. Subsequently detailed numerical PDR models are compared to these predictions, yielding additional insights into the dominant thermal processes in the PDRs and their structures. We find that the PDRs of each object are very similar, and can be characterized by a two-phase PDR model with a very dense, highly UV irradiated phase (n $\sim$ 10^6 cm^(-3), G$_0$ $\sim$ 10^5) interspersed within a lower density, weaker radiation field phase (n $\sim$ 10^4 cm^(-3), G$_0$ $\sim$ 10^4). We employed two different numerical models to investigate the data, firstly we used RADEX models to fit the peak of the $^{12}$CO ladder, which in conjunction with the properties derived yielded a temperature of around 300 K. Subsequent numerical modeling with a full PDR model revealed that the dense phase has a filling factor of around 0.6 in both objects. The shape of the $^{12}$CO ladder was consistent with these components with heating dominated by grain photoelectric heating. An extra excitation component for the highest J lines (J > 20) is required for S 106., Comment: 20 pages, 10 figures, A&A Accepted

The aromatic infrared bands (AIBs) observed in the mid infrared spectrum are attributed to Polycyclic Aromatic Hydrocarbons (PAHs). We observe the NGC 7023-North West (NW) PDR in the mid-infrared (10 - 19.5 micron) using the Infrared Spectrometer (IRS), on board Spitzer. Clear variations are observed in the spectra, most notably the ratio of the 11.0 to 11.2 micron bands, the peak position of the 11.2 and 12.0 micron bands, and the degree of asymmetry of the 11.2 micron band. The observed variations appear to change as a function of position within the PDR. We aim to explain these variations by a change in the abundances of the emitting components of the PDR. A Blind Signal Separation (BSS) method, i.e. a Non-Negative Matrix Factorization algorithm is applied to separate the observed spectrum into components. Using the NASA Ames PAH IR Spectroscopic Database, these extracted signals are fit. The observed signals alone were also fit using the database and these components are compared to the BSS components. Three component signals were extracted from the observation using BSS. We attribute the three signals to ionized PAHs, neutral PAHs, and Very Small Grains (VSGs). The fit of the BSS extracted spectra with the PAH database further confirms the attribution to ionized and neutral PAHs and provides confidence in both methods for producing reliable results. The 11.0 micron feature is attributed to PAH cations while the 11.2 micron band is attributed to neutral PAHs. The VSG signal shows a characteristically asymmetric broad feature at 11.3 micron with an extended red wing. By combining the NASA Ames PAH IR Spectroscopic Database fit with the BSS method, the independent results of each method can be confirmed and some limitations of each method are overcome.

Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7 $\mu$m (1905 and 1754 cm$^{\rm - 1}$) that hitherto have been little studied, but contain information about the astronomical PAH population that complements that of the major emission bands. Here we report a study involving both laboratory and theoretical analysis of the fundamentals of PAH spectroscopy that produce features in this region and use these to analyze the astronomical spectra. The ISO SWS spectra of fifteen objects showing these PAH features were considered for this study, of which four have sufficient S/N between 5 and 6 $\mu$m to allow for an in-depth analysis. All four astronomical spectra show similar peak positions and profiles. The 5.25 $\mu$m feature is peaked and asymmetric, while the 5.7 $\mu$m feature is broader and flatter. Detailed analysis of the laboratory spectra and quantum chemical calculations show that the astronomical 5.25 and 5.7 $\mu$m bands are a blend of combination, difference and overtone bands primarily involving CH stretching and CH in-plane and CH out-of-plane bending fundamental vibrations. The experimental and computational spectra show that, of all the hydrogen adjacency classes possible on PAHs, solo and duo hydrogens consistently produce prominent bands at the observed positions whereas quartet hydrogens do not. In all, this a study supports the picture that astronomical PAHs are large with compact, regular structures. From the coupling with primarily strong CH out-of-plane bending modes one might surmise that the 5.25 and 5.7 $\mu$m bands track the neutral PAH population. However, theory suggests the role of charge in these astronomical bands might also be important., Comment: Accepted ApJ, 40 pages in pre-print, 14 figures, two online

Herbig Ae/Be stars are a class of young pre-main sequence stellar objects of intermediate mass and are known to have varying amounts of natal cloud material still present in their direct vicinity. We characterise the IR emission bands, due to fluorescence by PAH molecules, in the spectra of Herbig Ae/Be stars and link observed variations to spatial aspects of the mid-IR emission. We analysed two PAH dominated spectra from a sample of 15 Herbig Ae/Be stars observed with Spitzer and derive profiles of the major PAH bands. The shape and the measured band characteristics show pronounced variations between the two Spitzer spectra. Those variations parallel those found between three ISO spectra of other, well-studied, Herbig Ae/Be stars. The derived profiles are compared to those from a broad sample of sources. The Spitzer and ISO spectra exhibit characteristics commonly interpreted respectively as interstellar matter-like (ISM), non-ISM-like, or a combination of the two. We argue that the PAH emission detected from the sources exhibiting a combination of ISM-like and non-ISM-like characteristics indicates the presence of two dissimilar, spatially separated, PAH families. As the shape of the individual PAH band profiles reflects the composition of the PAH molecules involved, this demonstrates that PAHs in subsequent, evolutionary linked stages of star formation are different from those in the general ISM, implying active chemistry. None of the detected PAH emission can be associated with the (unresolved) disk and is thus associated with the circumstellar cloud. This implies that chemical changes may already occur in the natal cloud and not necessarily in the disk.

We present results from a survey for gravitationally lensed radio lobes. Lensed lobes are a potentially richer source of information about galaxy mass distributions than lensed point sources, which have been the exclusive focus of other recent surveys. Our approach is to identify radio lobes in the FIRST catalog and then search optical catalogs for coincident foreground galaxies, which are candidate lensing galaxies. We then obtain higher-resolution images of these targets at both optical and radio wavelengths, and obtain optical spectra for the most promising candidates. We present maps of several radio lobes that are nearly coincident with galaxies. We have not found any new and unambiguous cases of gravitational lensing. One radio lobe in particular, FOV J0743+1553, has two hot spots that could be multiple images produced by a z=0.19 spiral galaxy, but the lensing interpretation is problematic., Comment: 38 pages, 18 figures, aastex, accepted to AJ