arXiv subjects

L. J. Allamandola

Publications and source records attributed to L. J. Allamandola.

At least 19 recordsLinked to original sources

arXiv2023

JWST: Deuterated PAHs, PAH-nitriles, and PAH Overtone and Combination Bands I: Program Description and First Look

A first look is taken at the NIRSpec 1-5 $μ$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 $μ$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 $μ$m (FWHM=0.04 $μ$m). Signs of its 1.68 $μ$m overtone are confused by line emission in all targets. Multi-component decomposition reveals a possible aliphatic deuterated PAH feature centered at 4.65 $μ$m (FWHM=0.02 $μ$m), giving [D/H]$_{\rm alip.}$=31$\pm$12.7%. However, there is little sign of its aromatic counterpart between 4.36-4.43 $μ$m. There is also little sign of PAH-nitrile emission between 4.34-4.39 $μ$m. A PAH continuum rises from $\sim$1 to 3.2 $μ$m, after which it jumps by about a factor of 2.5 at 3.6 $μ$m, with bumps at 3.8, 4.04, and 4.34 $μ$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 $>$30. Considering Br$α$/Br$β$=0.381$\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.

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arXiv2022

Linking Characteristics of the Polycyclic Aromatic Hydrocarbon Population with Galaxy Properties: A Quantitative Approach Using the NASA Ames PAH IR Spectroscopic Database

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 $μ$m PAH ratio with the ionization parameter ($γ\equiv(G_{0}/n_{\rm e})(T_{\rm gas} / 1\ \mathrm{K})^{0.5}$), a moderate correlation between the 8.6/11.2 $μ$m PAH ratio and specific star-formation rate, and a weak anti-correlation between $γ$ and M$_{*}$. From the PAHdb decomposition we provide estimates for the 3.3 $μ$m PAH band, not covered by Spitzer observations, and establish a correlation between the 3.3/11.2 $μ$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.

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arXiv2021

PAH Spectroscopy from 1-5 $μ$m

The PAH model predicts many weak emission features in the 1-5 $μ$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 $μ$m region. Apart from the 3.3 $μ$m band and plateau, PAH spectroscopy across most of the 1-5 $μ$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 $μ$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 $μ$m that arise from CD versus C$\equiv$N.

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arXiv2016

Polycyclic Aromatic Hydrocarbon emission in Spitzer/IRS maps I: Catalog and simple diagnostics

We present a sample of resolved galactic HII regions and photodissociation regions (PDRs) observed with the Spitzer infrared spectrograph (IRS) in spectral mapping mode between the wavelengths of 5--15 $μ$m. For each object we have spectral maps at a spatial resolution of $\sim$4" in which we have measured all of the mid-infrared emission and absorption features. These include the PAH emission bands, primarily at 6.2, 7.7, 8.6, 11.2 and 12.7 $μ$m, as well as the spectral emission lines of neon and sulfur and the absorption band caused by silicate dust at around 9.8 $μ$m. In this work we describe the data in detail, including the data reduction and measurement strategies, and subsequently present the PAH emission band intensity correlations for each of the objects and the sample as a whole. We find that there are distinct differences between the sources in the sample, with two main groups, the first comprising the HII regions and the second the reflection nebulae (RNe). Three sources, the reflection nebula NGC~7023, the Horsehead nebula PDR (an interface between the HII region IC~434 and the Orion B molecular cloud) and M 17, resist this categorization, with the Horsehead PDR points mimicking the RNe and the NGC~7023 fluxes displaying unique bifurcated appearance in our correlation plots. These discrepancies seem to be due to the very low radiation field experienced by the Horsehead PDR and the very clean separation between the PDR environment and a diffuse environment in the NGC~7023 observations.

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arXiv2014

Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices

Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 microns) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate the search for frozen interstellar PAHs, laboratory experiments were conducted to determine the positions and strengths of the bands of pyrene mixed with H2O and D2O ices. The D2O mixtures are used to measure pyrene bands that are masked by the strong bands of H2O, leading to the first laboratory determination of the band strength for the CH stretching mode of pyrene in water ice near 3.25 microns. Our infrared band strengths were normalized to experimentally determined ultraviolet band strengths, and we find that they are generally ~50% larger than those reported by Bouwman et al. based on theoretical strengths. These improved band strengths were used to reexamine YSO spectra published by Boogert et al. to estimate the contribution of frozen PAHs to absorption in the 5-8 micron spectral region, taking into account the strength of the 3.25 micron CH stretching mode. It is found that frozen neutral PAHs contain 5%-9% of the cosmic carbon budget, and account for 2%-9% of the unidentified absorption in the 5-8 micron region.

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arXiv2011

Coupled Blind Signal Separation and Spectroscopic Database Fitting of the Mid Infrared PAH Features

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.

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arXiv2011

Ices in the Quiescent IC 5146 Dense Cloud

This paper presents spectra in the 2 to 20 micron range of quiescent cloud material located in the IC 5146 cloud complex. The spectra were obtained with NASA's Infrared Telescope Facility (IRTF) SpeX instrument and the Spitzer Space Telescope's Infrared Spectrometer. We use these spectra to investigate dust and ice absorption features in pristine regions of the cloud that are unaltered by embedded stars. We find that the H2O-ice threshold extinction is 4.03+/-0.05 mag. Once foreground extinction is taken into account, however, the threshold drops to 3.2 mag, equivalent to that found for the Taurus dark cloud, generally assumed to be the touchstone quiescent cloud against which all other dense cloud and embedded young stellar object observations are compared. Substructure in the trough of the silicate band for two sources is attributed to CH3OH and NH3 in the ices, present at the ~2% and ~5% levels, respectively, relative to H2O-ice. The correlation of the silicate feature with the E(J-K) color excess is found to follow a much shallower slope relative to lines of sight that probe diffuse clouds, supporting the previous results by Chiar et al. (2007).

astro-ph.GA↗

arXiv2009

Photochemistry of the PAH pyrene in water ice: the case for ion-mediated solid-state astrochemistry

Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, \water and CO. Pyrene ionisation is found to be most efficient in \water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.

astro-ph.SR↗

arXiv2009

Real-time optical spectroscopy of VUV irradiated pyrene:H_2O interstellar ice

This paper describes a near-UV/VIS study of a pyrene:H_2O interstellar ice analogue at 10 K using optical absorption spectroscopy. A new experimental approach makes it possible to irradiate the sample with vacuum ultraviolet (VUV) light (7-10.5 eV) while simultaneously recording spectra in the 240-1000 nm range with subsecond time resolution. Both spectroscopic and dynamic information on VUV processed ices are obtained in this way. This provides a powerful tool to follow, in-situ and in real time, the photophysical and photochemical processes induced by VUV irradiation of a polycyclic aromatic hydrocarbon containing inter- and circumstellar ice analogue. Results on the VUV photolysis of a prototype sample - strongly diluted pyrene in H_2O ice - are presented. In addition to the pyrene cation (Py+), other products - hydroxypyrene (PyOH), possibly hydroxypyrene cation (PyOH+), and pyrene/pyrenolate anion (Py-/PyO-) - are observed. It is found that the charge remains localized in the ice, also after the VUV irradiation is stopped. The astrochemical implications and observational constraints are discussed.

astro-ph.IM↗

arXiv2008

The 5.25 & 5.7 $μ$m Astronomical Polycyclic Aromatic Hydrocarbon Emission Features

Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7 $μ$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 $μ$m to allow for an in-depth analysis. All four astronomical spectra show similar peak positions and profiles. The 5.25 $μ$m feature is peaked and asymmetric, while the 5.7 $μ$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 $μ$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 $μ$m bands track the neutral PAH population. However, theory suggests the role of charge in these astronomical bands might also be important.

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arXiv2005

The 15-21 um PAH plateau

We present 14--21 um emission spectra of star forming regions and compare them with the PAH spectra from the Ames PAH database. We show that while the emission in this region can be quite variable, the bulk of these variations can be accommodated by variations in the IS PAH population.

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arXiv2004

The profiles of the 3 to 12 $μ$m PAH features

We present spectra of the 3.3 $μ$m and 11.2 $μ$m PAH features of a large number of (extra-) galactic sources, obtained with ISO-SWS. Clear variations are present in the profiles of these features. The sources are classified independently based on the 3.3 and 11.2 $μ$m feature profiles and peak positions. Correlations between these classes and those based on the 6--9 $μ$m features (Peeters et al. 2002) are found. Also, these classifications depend on the type of object. The observed pronounced contrast in the spectral variations for the CH modes (3.3 and 11.2 $μ$m bands) versus the CC modes (6.2, 7.7 and 8.6 $μ$m bands) is striking : the peak wavelengths of the features attributed to CC modes vary by $\sim$15--80 cm$^{-1}$, while for the CH modes the variations are $\sim$4--6.5 cm$^{-1}$. We summarize existing laboratory data and theoretical calculations of PAH molecules and complexes. In contrast to the 6.2 and 7.7 $μ$m components which are attributed to PAH cations, the 3.3 $μ$m feature appears to originate in neutral and/or negatively charged PAHs. We attribute the variations in peak position and profile of these features to the composition of the PAH family. The variations in FWHM of the 3.3 $μ$m feature remains an enigma while those of the 11.2 $μ$m 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.

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arXiv2003

The Unidentified InfraRed Features after ISO

The Infrared Space Observatory (ISO) has provided the first complete mid-IR spectra for a wide range of objects. Almost all of these spectra are dominated by the well-known infrared emission features at 3.3, 6.2, 7.7, and 11.2 $μ$m, the so-called Unidentified Infra-Red (UIR) features. Besides the major features, there is an array of minor features and broad plateaux stretching from 3 to 20 $μ$m which reveal subtle details of conditions in the emission zones and properties of the carriers. Generally attributed to the vibrational relaxation of UV-pumped Polycyclic Aromatic Hydrocarbon molecules (PAHs) containing some 50--100 C-atoms, these UIR spectra are a treasure trove of information. The ISO spectra have, for the first time, allowed a systematic analysis of the spectral characteristics of the UIR features in a wide variety of environments. The peak positions, profiles, and relative strengths of the major features vary from source to source and spatially within sources. These specific profiles are not unique to certain object types but can occur within each individual source. Here, we review ISO and recent ground-based observations and assess some of their implications.

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arXiv2003

The Role of Polycyclic Aromatic Hydrocarbons in Ultraviolet Extinction. I. Probing small molecular PAHs

We have obtained new STIS/HST spectra to search for structure in the ultraviolet interstellar extinction curve, with particular emphasis on a search for absorption features produced by polycyclic aromatic hydrocarbons (PAHs). The presence of these molecules in the interstellar medium has been postulated to explain the infrared emission features seen in the 3-13 $μ$m spectra of numerous sources. UV spectra are uniquely capable of identifying specific PAH molecules. We obtained high S/N UV spectra of stars which are significantly more reddened than those observed in previous studies. These data put limits on the role of small (30-50 carbon atoms) PAHs in UV extinction and call for further observations to probe the role of larger PAHs. PAHs are of importance because of their ubiquity and high abundance inferred from the infrared data and also because they may link the molecular and dust phases of the interstellar medium. A presence or absence of ultraviolet absorption bands due to PAHs could be a definitive test of this hypothesis. We should be able to detect a 20 Åwide feature down to a 3$σ$ limit of $\sim$0.02 A$_V$. No such absorption features are seen other than the well-known 2175 Åbump.

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arXiv2002

The rich 6 to 9 um spectrum of interstellar PAHs

Here, we present 6-9 um spectra of a sample of RNe, HII regions, YSOs, evolved stars and galaxies that show strong unidentified infrared bands, obtained with the ISO-SWS. The IR emission features show pronounced variations. 1) The 6.2 um feature shifts and clearly shows profile variations. 2) The 7.7 um complex is comprised of at least two subpeaks peaking at 7.6 and one longwards of 7.7 um. In some cases the main peak can apparently shift up to 8 um. Two sources do not exhibit a 7.7 um complex but instead show a broad emission feature at 8.22 um. 3) The 8.6 um feature has a symmetric profile in all sources and some sources exhibit this band at slightly longer wavelengths. For the 6.2, 7.7 and 8.6 um features, the sources have been classified independently based on their profile and peak position. The classes derived for these features are directly linked with each other. Furthermore, the observed 6--9 um spectrum depends on the type of object. We attribute the observed 6.2 um profile and peak position to the combined effect of a PAH family and anharmonicity with pure PAHs representing the 6.3 um component and substituted/complexed PAHs representing the 6.2 um component. The 7.6 um component is well reproduced by both pure and substituted/complexed PAHs but the 7.8 um component remains an enigma. In addition, the exact identification of the 8.22 um feature remains unknown. The observed variations in the characteristics of the IR emission bands are linked to the local physical conditions. Possible formation and evolution processes that may influence the interstellar PAH class are highlighted.

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arXiv2002

A New Feature in the Interstellar Extinction Curve at 2700 A: Diamonds in the Rough?

Space Telescope Imaging Spectrograph (STIS) and archival International Ultraviolet Explorer (IUE) data were used to search for structure in the ultraviolet interstellar extinction curve. Between 1250 and 3200 A, in addition to the well-known 2175 A bump, there is only one fairly small (10%) absorption feature at 2700 A. The feature is very broad (>400 A). It coincides extremely well in position and shape with laboratory measurements of presolar diamond grains found in meteorites. As this feature appears in both the new STIS and archival IUE data, it is unlikely to be an instrumental effect. This feature appears to be ubiquitous in the ISM as it is seen along sightlines toward various clouds with reddenings in the range of E(B-V) = 0.35 to 1.73 mag. The identification with diamonds remains tentative since it is based on a single, weak feature. If the feature is due to interstellar diamonds then they require an order of magnitude more absorption strength per gram/cm^2 than the presolar meteoritic diamonds measured in the lab.

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arXiv2001

The CH out-of-plane bending modes of PAH molecules in astrophysical environments

We present 10-15 micron spectra of a sample of H II regions, YSOs and evolved stars that show strong unidentified infrared emission features, obtained with the ISO/SWS spectrograph on-board ISO. These spectra reveal a plethora of emission features with bands at 11.0, 11.2, 12.0, 12.7, 13.5 and 14.2 micron. These features are observed to vary considerably in relative strength to each-other from source to source. In particular, the 10-15 micron spectra of the evolved stars are dominated by the 11.2 micron band while for H II regions the 12.7 is typically as strong as the 11.2 micron band. Analysing the ISO data we find a good correlation between the 11.2 micron band and the 3.3 micron band, and between the 12.7 micron and the 6.2 micron band. There is also a correlation between the ratio of the UIR bands to the total dust emission and the 12.7 over 11.2 micron ratio. Bands in the 10-15 micron spectral region are due to CH out-of-plane (OOP) bending modes of polycyclic aromatic hydrocarbons (PAHs). We summarise existing laboratory data and theoretical quantum chemical calculations of these modes for neutral and cationic PAHs. Due to mode coupling, the exact peak position of these bands depends on the number of adjacent CH groups and hence the observed interstellar 10-15 micron spectra can be used to determine the molecular structure of the interstellar PAHs emitting in the different regions. We conclude that evolved stars predominantly inject compact ~100-200 C-atom PAHs into the ISM where they are subsequently processed, resulting in more open and uneven PAH structures.

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arXiv1999

Direct spectroscopic evidence for ionized PAHs in the interstellar medium

Long-slit 8-13 um spectroscopy of the nebula around NGC 1333 SVS reveals spatial variations in the strength and shape of emission features which are probably produced by polycyclic aromatic hydrocarbons (PAHs). Close to SVS 3, the 11.2 um feature develops an excess at ~10.8-11.0 um, and a feature appears at ~10 um. These features disappear with increasing distance from the central source, and they show striking similarities to recent laboratory data of PAH cations, providing the first identification of emission features arising specifically from ionized PAHs in the interstellar medium.

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