Neutral Polycyclic Aromatic Hydrocarbons Research Articles

FEAST: Feedback in Emerging extragAlactic Star ClusTers: JWST Spots Polycyclic Aromatic Hydrocarbon Destruction in NGC 628 during the Emerging Phase of Star Formation

We investigate the emergence phase of young star clusters in the nearby spiral galaxy NGC 628. We use JWST NIRCam and MIRI observations to create spatially resolved maps of the Paα 1.87 μm and Brα 4.05 μm hydrogen recombination lines, as well as 3.3 and 7.7 μm emission from polycyclic aromatic hydrocarbons (PAHs). We extract 953 compact H ii regions and analyze the PAH emission and morphology at ∼10 pc scales in the associated photodissociation regions. While H ii regions remain compact, radial profiles help us to define three PAH morphological classes: compact (∼42%), extended (∼34%), and open (∼24%). The majority of compact and extended PAH morphologies are associated with very young star clusters (<5 Myr), while open PAH morphologies are mainly associated with star clusters older than 3 Myr. We observe a general decrease in the 3.3 and 7.7 μm PAH band emission as a function of cluster age, while their ratio remains constant with age out to 10 Myr and morphological class. The recovered PAH3.3μm/PAH7.7μm ratio is lower than values reported in the literature for reference models that consider neutral and ionized PAH populations and analyses conducted at galactic physical scales. The 3.3 and 7.7 μm bands are typically associated with neutral and ionized PAHs, respectively. While we expected neutral PAHs to be suppressed in proximity to an ionizing source, the constant PAH3.3μm/PAH7.7μm ratio would indicate that both families of molecules disrupt at similar rates in proximity to H ii regions.

Polycyclic aromatic hydrocarbon emission in galaxies as seen with JWST

ABSTRACT We present a systematic study of mid-infrared spectra of galaxies including star-forming galaxies and active galactic nuclei observed with JWST MIRI-MRS and NIRSpec-IFU. We focus on the relative variations of the 3.3, 6.2, 7.7, 11.3, 12.7, and 17 $\mu$m polycyclic aromatic hydrocarbon (PAH) features within spatially resolved regions of galaxies including NGC 3256, NGC 7469, VV 114, II Zw96, and NGC 5728. Using theoretical PAH models and extending our earlier work, we introduce a new PAH diagnostic involving the 17 $\mu$m PAH feature. To determine the drivers of PAH band variations in galaxies, we compare observed PAH spectral bands to predictions from theoretical PAH models. We consider extinction, dehydrogenation, and PAH size and charge as possible drivers of PAH band variations. We find a surprising uniformity in PAH size distribution among the spatially resolved regions of the galaxies studied here, with no evidence for preferential destruction of the smallest grains, contrary to earlier findings. Neither extinction nor dehydrogenation play a crucial role in setting the observed PAH bands. Instead, we find that PAH charge plays a significant role in PAH inter-band variations. We find a tight relation between PAH charge and the intensity of the radiation field as traced by the [Ne iii]$/$[Ne ii] maps. In agreement with recent JWST results, we find a predominance of neutral PAH molecules in the nuclei of active galaxies and their outflows. Ionized PAHs are the dominant population in star-forming galaxies. We discuss the implications of our findings for the use of PAHs as ISM tracers in high redshift galaxies.

Polycyclic aromatic hydrocarbon emission in galaxies as seen with JWST

ABSTRACT We present a systematic study of mid-infrared spectra of galaxies including star-forming galaxies and active galactic nuclei observed with JWST MIRI-MRS and NIRSpec-IFU. We focus on the relative variations of the 3.3, 6.2, 7.7, 11.3, 12.7, and 17 $\mu$m polycyclic aromatic hydrocarbon (PAH) features within spatially resolved regions of galaxies including NGC 3256, NGC 7469, VV 114, II Zw96, and NGC 5728. Using theoretical PAH models and extending our earlier work, we introduce a new PAH diagnostic involving the 17 $\mu$m PAH feature. To determine the drivers of PAH band variations in galaxies, we compare observed PAH spectral bands to predictions from theoretical PAH models. We consider extinction, dehydrogenation, and PAH size and charge as possible drivers of PAH band variations. We find a surprising uniformity in PAH size distribution among the spatially resolved regions of the galaxies studied here, with no evidence for preferential destruction of the smallest grains, contrary to earlier findings. Neither extinction nor dehydrogenation play a crucial role in setting the observed PAH bands. Instead, we find that PAH charge plays a significant role in PAH inter-band variations. We find a tight relation between PAH charge and the intensity of the radiation field as traced by the [Ne iii]$/$[Ne ii] maps. In agreement with recent JWST results, we find a predominance of neutral PAH molecules in the nuclei of active galaxies and their outflows. Ionized PAHs are the dominant population in star-forming galaxies. We discuss the implications of our findings for the use of PAHs as ISM tracers in high redshift galaxies.

GOALS-JWST: Small Neutral Grains and Enhanced 3.3 μm PAH Emission in the Seyfert Galaxy NGC 7469

We present James Webb Space Telescope (JWST) Near Infrared Spectrograph (NIRSpec) integral field spectroscopy of the nearby luminous infrared galaxy NGC 7469. We take advantage of the high spatial/spectral resolution and wavelength coverage of JWST/NIRSpec to study the 3.3 μm neutral polycyclic aromatic hydrocarbon (PAH) grain emission on ∼200 pc scales. A clear change in the average grain properties between the star-forming ring and the central AGN is found. Regions in the vicinity of the AGN, with [Ne iii]/[Ne ii] > 0.25, tend to have larger grain sizes and lower aliphatic-to-aromatic (3.4/3.3) ratios, indicating that smaller grains are preferentially removed by photodestruction in the vicinity of the AGN. PAH emission at the nucleus is weak and shows a low 11.3/3.3 PAH ratio. We find an overall suppression of the total PAH emission relative to the ionized gas in the central 1 kpc region of the AGN in NGC 7469 compared to what has been observed with Spitzer on 3 kpc scales. However, the fractional 3.3 μm–to–total PAH power is enhanced in the starburst ring, possibly due to a variety of physical effects on subkiloparsec scales, including recurrent fluorescence of small grains or multiple photon absorption by large grains. Finally, the IFU data show that while the 3.3 μm PAH-derived star formation rate (SFR) in the ring is 27% higher than that inferred from the [Ne ii] and [Ne iii] emission lines, the integrated SFR derived from the 3.3 μm feature would be underestimated by a factor of 2 due to the deficit of PAHs around the AGN, as might occur if a composite system like NGC 7469 were to be observed at high redshift.

Anharmonic IR absorption spectra of the prototypical interstellar PAHs phenanthrene, pyrene, and pentacene in their neutral and cation states

Combination band and overtone transitions of polycyclic aromatic hydrocarbon (PAH) cations in the 2000–2900 cm-1 (5-3.5 µm) region are implicated as carriers of the ‘quasi-continuum’ observed in the near-infrared (IR) emission spectra of many astronomical objects. In neutral PAHs, the strongest absorption features are concentrated in the 700–900 cm-1 (14–11 µm) range, which are associated with CH out-of-plane bending motions. Upon ionization, this shifts to the 1000–1600 cm-1 (10–6 µm) range, where bands are associated with C=C stretches and CH in-plane bends. Anharmonicity is required to accurately characterize the IR absorption spectrum of PAHs, indicated herein by the ability to directly assign the bands in high-resolution experimental absorption spectra of neutral and cationic phenanthrene, pyrene, and pentacene. Neutral PAHs are indicated as the source of the strong 3.3 and 11.2 µm astronomical PAH features, while the broad features in the 6–10 µm region and the ‘quasi-continuum’ from 3.5–5 µm stem from PAH cations. This study reinforces the need for including anharmonicity in the computation of IR absorption and emission spectra of larger and more complex PAHs. This is particularly pertinent to the interpretation of data returned by JWST.

Machine learning identified molecular fragments responsible for infrared emission features of polycyclic aromatic hydrocarbons

ABSTRACT Machine learning feature importance calculations are used to determine the molecular substructures that are responsible for mid- and far-infrared (IR) emission features of neutral polycyclic aromatic hydrocarbons (PAHs). Using the extended-connectivity fingerprint as a descriptor of chemical structure, a random forest model is trained on the spectra of 14 124 PAHs to evaluate the importance of 10 632 molecular fragments for each band within the range of 2.761 to $1172.745\, \mu$m. The accuracy of the results is confirmed by comparing them with previously studied unidentified infrared emission (UIE) bands. The results are summarized in two tables available as Supplementary Data, which can be used as a reference for assessing possible UIE carriers. We demonstrate that the tables can be used to explore the relation between the PAH structure and the spectra by discussing about the IR features of nitrogen-containing PAHs and superhydrogenated PAHs.

PHANGS–JWST First Results: Variations in PAH Fraction as a Function of ISM Phase and Metallicity

We present maps tracing the fraction of dust in the form of polycyclic aromatic hydrocarbons (PAHs) in IC 5332, NGC 628, NGC 1365, and NGC 7496 from JWST/MIRI observations. We trace the PAH fraction by combining the F770W (7.7 μm) and F1130W (11.3 μm) filters to track ionized and neutral PAH emission, respectively, and comparing the PAH emission to F2100W, which traces small, hot dust grains. We find the average R PAH = (F770W + F1130W)/F2100W values of 3.3, 4.7, 5.1, and 3.6 in IC 5332, NGC 628, NGC 1365, and NGC 7496, respectively. We find that H ii regions traced by MUSE Hα show a systematically low PAH fraction. The PAH fraction remains relatively constant across other galactic environments, with slight variations. We use CO+Hi +Hα to trace the interstellar gas phase and find that the PAH fraction decreases above a value of in all four galaxies. Radial profiles also show a decreasing PAH fraction with increasing radius, correlated with lower metallicity, in line with previous results showing a strong metallicity dependence to the PAH fraction. Our results suggest that the process of PAH destruction in ionized gas operates similarly across the four targets.

A high angular resolution view of the PAH emission in Seyfert galaxies using JWST/MRS data

Polycyclic aromatic hydrocarbons (PAHs) are carbon-based molecules that are ubiquitous in a variety of astrophysical objects and environments. In this work we use JWST/MIRI MRS spectroscopy of three Seyferts to compare their nuclear PAH emission with that of star-forming (SF) regions. This study represents the first of its kind to use sub-arcsecond angular resolution data of local luminous Seyferts (Lbol &gt; 1044.46 erg s−1) with a wide wavelength coverage (4.9–28.1 μm). We present an analysis of their nuclear PAH properties by comparing the observed ratios with PAH diagnostic model grids derived from theoretical spectra. Our results show that a suite of PAH features is present in the innermost parts of luminous Seyfert galaxies (∼0.45″ at 12 μm; in the inner ∼142–245 pc). We find that the nuclear regions of active galactic nuclei (AGN) lie at different positions of the PAH diagnostic diagrams, whereas the SF regions are concentrated around the average values of SF galaxies. In particular, we find that the nuclear PAH emission mainly originates in neutral PAHs. In contrast, PAH emission originating in the SF regions favours ionised PAH grains. The observed PAH ratios in the nuclear region of the AGN-dominated galaxy NGC 6552 indicate the presence of larger PAH molecules compared with those of the SF regions. Therefore, our results provide evidence that the AGN have a significant impact on the ionisation state (and probably the size) of the PAH grains on scales of ∼142–245 pc.

Gas-phase reaction of fullerene monocations with 2,3-benzofluorene indicates the importance of charge exchanges

Fullerene and polycyclic aromatic hydrocarbon (PAH) molecules, as well as their cations and clusters, are of great interest in astrochemistry. In this work, the ion-molecule collision reaction between fullerene (e.g. a C54/56/58 and C60 system or a C64/66/68 and C70 system) monocations and neutral PAHs (e.g. 2,3-benzofluorene, C17H12) is studied in the gas phase to determine the importance of charge exchanges and to illustrate the competition between charge transfer and molecular adduct formation channels. The experimental results show that the charge transfer channel is the dominant channel (i.e. charge exchange) in the reaction between fullerene (C60 and C70) monocations and 2,3-benzofluorene, while the molecular adduct formation channels are the dominant channels in the reaction between fullerene (C54/56/58 and C64/66/68) monocations and 2,3-benzofluorene. The observed reaction behaviours are investigated with quantum calculations, and the CH2 unit binding effect of 2,3-benzofluorene is determined to be the main reason for the results. Our findings on the ion-molecule collision reaction between fullerene monocations and 2,3-benzofluorene provide a good model for understanding the physical-chemical processes of the charge transfer channel and the cluster adduct formation channels. Neutral fullerenes (C60 and C70) increase the abundance of their monocations through collision reactions with coexisting neutral molecules in the interstellar medium.

Theoretical study of infrared spectra of interstellar PAH molecules with N, NH, and NH2 incorporation

Abstract This work presents theoretical calculations of infrared spectra of nitrogen (N)-containing polycyclic aromatic hydrocarbon (PAH) molecules with the incorporation of N, NH, and NH2 using density functional theory (DFT). The properties of their vibrational modes in 2–15 μm are investigated in relation to the Unidentified Infrared (UIR) bands. It is found that neutral PAHs, when incorporated with NH2 and N (at inner positions), produce intense infrared bands at 6.2, 7.7, and 8.6 μm that have been normally attributed to ionized PAHs so far. The present results suggest that strong bands at 6.2 and 11.2 μm can arise from the same charge state of some N-containing PAHs, arguing that there might be some N-abundant astronomical regions where the 6.2 to 11.2 μm band ratio is not a direct indicator of the PAHs’ ionization. PAHs with NH2 and N inside the carbon structure show the UIR band features characteristic to star-forming regions as well as reflection nebulae (Class A), whereas PAHs with N at the periphery have similar spectra to the UIR bands seen in planetary nebulae and post-AGB stars (Class B). The presence of N atoms at the periphery of a PAH may attract H or H+ to form N–H and N–H2 bonds, exhibiting features near 2.9–3.0 μm, which are not yet observationally detected. The absence of such features in the observations constrains the contribution of NH and NH2 substituted PAHs that could be better tested with concentrated observations in this range. However, PAHs with N without H either at the periphery or inside the carbon structure do not have the abundance constraint due to the absence of 2.9–3.0 μm features and are relevant in terms of positions of the UIR bands. Extensive theoretical and experimental studies are required to obtain deeper insight.

Orion Bar as a window to the evolution of PAHs

ABSTRACT We investigate the mid-infrared (IR) emission in the Orion Bar photodissociation region (PDR), using archival photometric and spectroscopic observations from the United Kingdom Infrared Telescope (UKIRT), Spitzer, Infrared Space Observatory(ISO), and Stratospheric Observatory for Infrared Astronomy (SOFIA) telescopes. Specifically, we consider flux densities of the emission bands at 3.3, 3.4, 3.6, 6.6, 7.7, and 11.2 $\mu$m in several locations and a spectrum from 3 to 45 $\mu$m in one location. We study the behaviour of band flux ratios, which are sensitive to external conditions, as revealed by their variations with the distance from an ionizing source. Assuming that the mid-IR emission arises mostly from polycyclic aromatic hydrocarbons (PAHs), and that a weak emission feature at 3.4 $\mu$m is related to PAHs with extra hydrogen atoms (H-PAHs), we trace variations of the ratios using a model for PAH evolution. Namely, we estimate how populations of PAHs of different sizes, hydrogenation and ionization states change across the Orion Bar over a time interval approximately equal to its lifetime. The obtained ensembles of PAHs are further used to calculate the corresponding synthetic spectra and band flux densities. The model satisfactorily describes the main features of the ratios I3.6/I11.2, I7.7/I11.2, I7.7/I3.6, and I3.3/I3.4. We conclude that the best coincidence between modelling and observations is achieved if C loss of PAHs is limited by the number of carbon atoms NC = 60, and the band at 3.4 $\mu$m may indeed be attributed to H-PAHs. We confirm that large cations dominate at the surface of the PDR but small neutral PAHs and anions are abundant deeper in the molecular cloud.

Infrared spectra of neutral polycyclic aromatic hydrocarbons based on machine learning potential energy surface and dipole mapping

The Interest in polycyclic aromatic hydrocarbons (PAHs) spans numerous fields and infrared spectroscopy is usually the method of choice to disentangle their molecular structure. In order to compute vibrational frequencies, numerous theoretical studies employ either quantum calculation methods, or empirical potentials, but it remains difficult to combine the accuracy of the first approach with the computational cost of the second. In this work, we employed Machine Learning techniques to develop a potential energy surface and a dipole mapping based on an artificial neural network (ANN) architecture. Altogether, while trained on only 11 small PAH molecules, the obtained ANNs are able to retrieve the infrared spectra of those small molecules, but more importantly of 8 large PAHs different from the training set, thus demonstrating the transferability of our approach.

ВРАЩАТЕЛЬНЫЕ СПЕКТРЫ РЯДА ПОЛИЦИКЛИЧЕСКИХ АРОМАТИЧЕСКИХ УГЛЕВОДОРОДОВ

A theoretical study of the rotational spectra of a number of polycyclic aromatic hydrocarbons (PAHs) was carried out on the basis of quantum-chemical calculations by PRIRODA program in the PBE/3ζ approximation. Calculations are given for neutral molecules, their radical anions and radical cations in the rigid top approximation. Twelve neutral PAHs under study have no dipole moment and are not of interest for rotational spectroscopy. Thirteen neutral PAHs have a dipole moment not exceeding 0.09 Debye and, under certain conditions, can be studied in the microwave region. The remaining six compounds are PAHs with methyl and phenyl substituents, their dipole moments are 0.32-0.65 Debye, which makes it possible to study their microwave spectrum. For radical ions, the situation with the dipole moment is as follows: if a neutral molecule does not have a dipole moment, then the corresponding radical ion does not have it either; if the dipole moment of a neutral molecule is nonzero, then for radical ions it increases at least several times. For example, in the benzo [b] chrysene radical anion, the μa-component component of the dipole moment increases by 250 times, the μb-component by 7 times, and the total dipole moment by about 100 times. This effect is more pronounced for radical anions than for radical cations. In this case, it becomes possible to detect the spectrum of if not a neutral molecule, then at least one of its charge states. For a number of compounds, the patterns of various spectroscopic parameters depending on the number of carbon atoms in PAHs were found. In the B3LYP/6-31G(d,p) approximation, quartic centrifugal distortion constants were calculated for five compounds, and their effect on the rotational spectrum was estimated: for many compounds under study, they can have a significant effect on the microwave spectrum. With an increase in PAHs, the centrifugal constants decrease indicating an increase in the rigidity of the molecules. Thus, substituted neutral PAHs, as well as a number of radical ions, may be of interest for experimental studies in laboratory conditions and in space.

Assessment of the Presence of PAHs and Hydrogenated PAHs in the Young Stellar Object Mon R2 and the Taurus Dense Cloud Toward Elias 16

Abstract This study assesses the contribution of neutral polycyclic aromatic hydrocarbons (PAHs) and hydrogenated PAHs (H n -PAHs) in H2O-ices to the 3 μm and 5–8 μm regions of the infrared absorption spectrum of the Young Stellar Object, Mon R2 IRS 3, and the Taurus dense cloud in the direction of Elias 16. We compare the astronomical spectra to the previously published laboratory data of matrix-isolated PAHs and H n -PAHs in H2O-ices. For the molecules in this study, the band positions, FWHMs, and integrated band strengths have been measured. For the PAHs considered here, the ratio of the experimental A(C–H) stretch (in H2O ices) to the theoretical A(C–H) stretch (in the gas phase) is consistently about 0.10, meaning that the trove of theoretical data can be reliably scaled to compare to the astronomical spectra. We find that the fractional percentage contribution to the 5–8 μm region for Mon R2 IRS 3 ranges between 2.7 and 3.9 for neutral PAHs and 0.25–1.2 for H n -PAHs. The best match to the observed 3.25 μm profile in the Mon R2 IRS 3 spectrum is accomplished with the laboratory-measured coronene:H2O spectrum. Using this spectrum we estimate that neutral PAHs contribute up to 12.0% of the cosmic carbon budget for Mon R2 IRS 3 and &lt;14.5% for Elias 16. Neutral hydrogenated PAHs contribute mainly to the 3.47 μm absorption and very little to the 5 to 8 μm region. For neutral H n -PAHs, we estimate that they contribute up to 0.6% of the cosmic carbon budget for Mon R2 IRS 3 and &lt;1% for Elias 16.

Heavy Positive Ion Groups in Titan’s Ionosphere from Cassini Plasma Spectrometer IBS Observations

Abstract Titan’s ionosphere contains a plethora of hydrocarbons and nitrile cations and anions as measured by the Ion Neutral Mass Spectrometer and Cassini Plasma Spectrometer (CAPS) on board the Cassini spacecraft. Data from the CAPS Ion Beam Spectrometer (IBS) sensor have been examined for five close encounters of Titan during 2009. The high relative velocity of Cassini with respect to the cold ions in Titan’s ionosphere allows CAPS IBS to function as a mass spectrometer. Positive ion masses between 170 and 310 u/q are examined with ion mass groups identified between 170 and 275 u/q containing between 14 and 21 heavy (carbon/nitrogen/oxygen) atoms. These groups are the heaviest positive ion groups reported so far from the available in situ ion data at Titan. The ion group peaks are found to be consistent with masses associated with polycyclic aromatic compounds (PAC), including polycyclic aromatic hydrocarbon (PAH) and nitrogen-bearing polycyclic aromatic molecular ions. The ion group peak identifications are compared with previously proposed neutral PAHs and are found to be at similar masses, supporting a PAH interpretation. The spacing between the ion group peaks is also investigated, finding a spacing of 12 or 13 u/q indicating the addition of C or CH. Lastly, the occurrence of several ion groups is seen to vary across the five flybys studied, possibly relating to the varying solar radiation conditions observed across the flybys. These findings further the understanding between the low-mass ions and the high-mass negative ions, as well as with aerosol formation in Titan’s atmosphere.

Determining binding of polycyclic aromatic hydrocarbons to micelles formed by SDS and SOL using semi-equilibrium dialysis

Micellar enhanced ultra-filtration (MEUF) is a modified ultrafiltration (UF) method that can remove small molecules that are not effectively removed by UF alone. In this work we used a similar semi-equilibrium dialysis (SED) method to characterize two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium laurate (SOL), as MEUF candidates to remove several polycyclic aromatic hydrocarbon (PAH) compounds. These anionic surfactants have low toxicity and are more biodegradable compared to the fairly toxic and persistent cetyltrimethylammonium bromide (CTABr) and similar cationic surfactants, which is important as MEUF surfactants may be present in the treated effluent. The log binding constants (Log KB) of the PAHs naphthalene, phenanthrene, pyrene and fluorene to SDS ranged from 3.07 to 4.48, which compared well with the previous results for CTABr and indicated that SDS is an excellent candidate for MEUF. The log binding constants for the same PAHs with SOL micelles ranged from 2.11 to 3.53, which suggested that SOL might be adequate for stronger-binding PAH like pyrene and fluorene but less suitable for naphthalene and phenanthrene. The results demonstrated a strong correlation between the Log KB with one micelle type and the Log KB with the other, suggesting a common set of properties and interactions are responsible for the binding. Similar to the previous results for CTABr, a significant correlation between Log KB and Log KOW values indicates that hydrophobic character is the main driving force for PAH binding with these anionic micelles. This may also be useful for predicting MEUF performance for various compound/surfactant combinations where Log KB is not known.

Detection of PAH and nbL features in planetary nebulae NGC 7027 and BD +30° 3639 with TIRCAM2 instrument on 3.6 m DOT

High resolution infrared imaging observations of the young Planetary Nebulae NGC 7027 and BD +303639, taken with the newly installed TIFR Infrared Camera-II (TIRCAM2) on 3.6m Devasthal Optical Telescope (DOT), ARIES, Nainital, are being reported. The images are acquired in J, H, K, polycyclic aromatic hydrocarbon (PAH) and narrow-band L (nbL) filters. The observations show emission from warm dust and PAHs in the circumstellar shells. The imaging of the two objects are among the first observations in PAH and nbL bands using TIRCAM2 on DOT. The NGC 7027 images in all bands show similar elliptical morphology with ~6".7 and ~4".5 semi-major and semi-minor axes. Considering size up to 10% of peak value the nebula extends upto 8" from the central star revealing a multipolar evolution. The relatively cooler BD +303639 shows a rectangular-ring shaped nebula. In J and H bands it shows an angular diameter of ~8", while a smaller ~6".9 size is observed in K, PAH and nbL bands. The 3.28 micron emission indicates presence of PAHs at about 6000 and 5000 AU from the central stars in NGC 7027 and BD +303639 respectively. Analysis suggests domination of neutral PAHs in BD+303639, while in NGC 7027 there is higher ionization and more processed PAH population.

Deuterated Polycyclic Aromatic Hydrocarbons in the Interstellar Medium: The C–D Band Strengths of Monodeuterated Species

Abstract Deuterium (D) is one of the light elements created in the Big Bang. As the Galaxy evolves, the D/H abundance in the interstellar medium (ISM) decreases from its primordial value due to astration. However, the observed gas-phase D/H abundances of some sightlines in the local Galactic ISM are substantially lower than the expected reduction by astration. The missing D could have been depleted onto polycyclic aromatic hydrocarbon (PAH) molecules which are ubiquitous and abundant in interstellar regions. To quantitatively explore the hypothesis of PAHs as a possible reservoir of interstellar D, we quantum-chemically compute the infrared vibrational spectra of monodeuterated PAHs and their cations. We find that, as expected, when H in PAHs is replaced by D, the C–H stretching and bending modes at 3.3, 8.6, and 11.3 μm shift to longer wavelengths at ∼4.4, 11.4, and 15.4 μm, respectively, by a factor of ∼ , the difference in reduced mass between the C–H and C–D oscillators. From the computed spectra we derive the mean intrinsic band strengths of the 3.3 μm C–H stretch and 4.4 μm C–D stretch to be and for neutral deuterated PAHs which would dominate the interstellar emission at 3.3 and 4.4 μm. By comparing the computationally derived mean band-strength ratio of for neutral PAHs with the mean ratio of the observed intensities of , we find that the degree of deuteration (i.e., the fraction of peripheral atoms attached to C atoms in the form of D) is ∼2.4%, corresponding to a D enrichment of a factor of ∼1200 with respect to the interstellar D/H abundance.

Far-IR Absorption of Neutral Polycyclic Aromatic Hydrocarbons (PAHs): Light on the Mechanism of IR-UV Ion Dip Spectroscopy.

Gas-phase IR–UV double-resonance laser spectroscopy is an IR absorption technique that bridges the gap between experimental IR spectroscopy and theory. The IR experiments are used to directly evaluate predicted frequencies and potential energy surfaces as well as to probe the structure of isolated molecules. However, a detailed understanding of the underlying mechanisms is, especially in the far-IR regime, still far from complete, even though this is crucial for properly interpreting the recorded IR absorption spectra. Here, events occurring upon excitation to vibrational levels of polycyclic aromatic hydrocarbons by far-IR radiation from the FELIX free electron laser are followed using resonance-enhanced multiphoton ionization spectroscopy. These studies provide detailed insight into how ladder climbing and anharmonicity influence IR–UV spectroscopy and therefore the resulting IR signatures in the far-IR region. Moreover, the potential energy surfaces of these low-frequency delocalized modes are investigated and shown to have a strong harmonic character.

Cold molecular gas and PAH emission in the nuclear and circumnuclear regions of Seyfert galaxies

We investigate the relation between the detection of the 11.3 μm polycyclic aromatic hydrocarbon (PAH) feature in the nuclear (∼24−230 pc) regions of 22 nearby Seyfert galaxies and the properties of the cold molecular gas. For the former we use ground-based (0.3−0.6″ resolution) mid-infrared (mid-IR) spectroscopy. The cold molecular gas is traced by ALMA and NOEMA high (0.2−1.1″) angular resolution observations of the CO(2–1) transition. Galaxies with a nuclear detection of the 11.3 μm PAH feature contain more cold molecular gas (median 1.6 × 107 M⊙) and have higher column densities (N(H2) = 2 × 1023 cm−2) over the regions sampled by the mid-IR slits than those without a detection. This suggests that molecular gas plays a role in shielding the PAH molecules in the harsh environments of Seyfert nuclei. Choosing the PAH molecule naphthalene as an illustration, we compute its half-life in the nuclear regions of our sample when exposed to 2.5 keV hard X-ray photons. We estimate shorter half-lives for naphthalene in nuclei without a 11.3 μm PAH detection than in those with a detection. TheSpitzer/IRS PAH ratios on circumnuclear scales (∼4″ ∼ 0.25−1.3 kpc) are in between model predictions for neutral and partly ionized PAHs. However, Seyfert galaxies in our sample with the highest nuclear H2column densities are not generally closer to the neutral PAH tracks. This is because in the majority of our sample galaxies, the CO(2–1) emission in the inner ∼4″ is not centrally peaked and in some galaxies traces circumnuclear sites of strong star formation activity. Spatially resolved observations with the MIRI medium-resolution spectrograph on theJames WebbSpace Telescope will be able to distinguish the effects of an active galactic nucleus (AGN) and star formation on the PAH emission in nearby AGN.