The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 $μ$m ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs may have an aliphatic component as revealed by the detection in many UIE sources of the aliphatic C-H stretching feature at 3.4 $μ$m. The ratio of the observed intensity of the 3.4 $μ$m feature to that of the 3.3 $μ$m aromatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers. This requires the knowledge of the intrinsic oscillator strengths of the 3.3 $μ$m aromatic C-H stretch ($A_{3.3}$) and the 3.4 $μ$m aliphatic C-H stretch ($A_{3.4}$). Lacking experimental data on $A_{3.3}$ and $A_{3.4}$ for the UIE candidate materials, one often has to rely on quantum-chemical computations. Although the second-order Moller-Plesset (MP2) perturbation theory with a large basis set is more accurate than the B3LYP density functional theory, MP2 is computationally very demanding and impractical for large molecules. Based on methylated PAHs, we show here that, by scaling the band strengths computed at an inexpensive level (e.g., B3LYP/6-31G*) we are able to obtain band strengths as accurate as that computed at far more expensive levels (e.g., MP2/6-311+G(3df,3pd)).
The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 micrometer aromatic C--H stretching feature is often accompanied by a weaker feature at 3.4 micrometer. The latter is often thought to result from the C--H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of…
The role of aliphatic side groups on the formation of astronomical unidentified infrared emission (UIE) features is investigated by applying the density functional theory (DFT) to a series of molecules with mixed aliphatic-aromatic structures. The effects of introducing various aliphatic groups to a fixed polycyclic aromatic hydrocarbon (PAH) core (ovalene) are studied. Simulated spectra for each molecule are produced by applying a Drude profile at $T$=500 K while the molecule is kept at its electronic ground state. The vibrational normal modes are classified using a semi-quantitative method. …
The "unidentified" infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 $μ$m are ubiquitously seen in various astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbons. The 3.3 $μ$m feature resulting from aromatic C--H stretches is often accompanied by a weaker feature at 3.4 $μ$m often attributed to aliphatic C--H stretches. The ratio of the observed intensity of the 3.3 $μ$m aromatic C--H feature ($I_{3.3}$) to that of the 3.4 $μ$m aliphatic C--H feature ($I_{3.4}$) allows one to estimate the aliphatic fraction (i…
The interaction of polycyclic aromatic hydrocarbons (PAHs) with vacuum ultraviolet (VUV) photons triggers the emission of the well-known aromatic infrared bands (AIBs) but other mechanisms such as fragmentation can be involved in this interaction. Fragmentation leads to selection effects that favor specific sizes and structures. We investigate the impact of aliphatic bonds on the VUV photo-stability of PAH cations under conditions applicable for photodissociation regions (PDRs). Cations of pyrene (C16H10) and coronene (C24H12) derivatives containing aliphatic bonds (methyl or ethyl sidegroups,…
The Influence of Aliphatic Components on the Aromatic Emission Characteristics of Polycyclic Aromatic Hydrocarbons
School of Physics and Astronomy, Sun Yat-sen University（中山大学物理学院）；CSST Science Center for the Guangdong-Hong Kong-Macau Greater Bay Area, Sun Yat-Sen University（中山大学粤港澳大湾区空间望远镜科学中心）
The unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to coal- or kerogen-like organic nanoparticles with a mixed aromatic-aliphatic structure. However, we show in this Letter that this hypothesis is inconsistent with observations. We estimate the aliphatic fraction of the UIE carriers based on the observed intensities of the 3.4 and 6.85 micrometer emission features by attributing them exclusively to aliphatic C-H stretch and aliphatic C-H deformation vib…
In photon-dominated regions (PDRs), UV photons from nearby stars lead to the evaporation of very small grains (VSGs) and the production of gas-phase polycyclic aromatic hydrocarbons (PAHs). Our goal is to achieve better insight into the composition and evolution of evaporating very small grains (eVSGs) and PAHs through analyzing the infrared (IR) aliphatic and aromatic emission bands. We combined spectro-imagery in the near- and mid-IR to study the spatial evolution of the emission bands in the prototypical PDR NGC 7023. We used near-IR spectra obtained with AKARI to trace the evolution of the…
We suggest that the carrier of the unidentified infrared emission (UIE) bands is an amorphous carbonaceous solid with mixed aromatic/aliphatic structures, rather than free-flying polycyclic aromatic hydrocarbon (PAH) molecules. Through spectral fittings of the astronomical spectra of the UIE bands, we show that a significant amount of the energy is emitted by the aliphatic component, implying that aliphatic groups are an essential part of the chemical structure. Arguments in favor of an amorphous, solid-state structure rather than a gas-phase molecule as a carrier of the UIE are also presented…
The amount of deuterium locked up in polycyclic aromatic hydrocarbons (PAHs) has to date been an uncertain value. We present a near-infrared (NIR) spectroscopic survey of HII regions in the Milky Way, Large Magellanic Cloud (LMC), and Small Magellanic Cloud (SMC) obtained with AKARI, which aims to search for features indicative of deuterated PAHs (PAD or Dn-PAH) to better constrain the D/H ratio of PAHs. Fifty-three HII regions were observed in the NIR (2.5-5 μm), using the Infrared Camera (IRC) on board the AKARI satellite. Through comparison of the observed spectra with a theoretical model o…
Aims. We aim to elucidate the spectral changes in the 3 micron region that result from chemical changes in the molecular periphery of polycyclic aromatic hydrocarbons (PAHs) with extra hydrogens (H-PAHs) and methyl groups (Me-PAHs). Methods. Advanced laser spectroscopic techniques combined with mass spectrometry were applied on supersonically cooled 1,2,3,4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenathrene, 1,2,3,6,7,8-hexahydropyrene, 9-methylanthracene, and 9,10-dimethylanthracene, allowing us to record mass-selective and conformationally selective absorption spectra of …
Although it is generally accepted that the so-called "unidentified" infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, the exact nature of their carriers remains unknown: whether they are free-flying, predominantly aromatic gas-phase molecules, or amorphous solids with a mixed aromatic/aliphatic composition are being debated. Recently, the 3.3 and 3.4 micrometer features which are commonly respectively attributed to aromatic and aliphatic C-H stretches have been used to place…
Aims. We investigate the properties of hydrocarbon grains in the galactic superwind of M 82. Methods. With AKARI, we performed near-infrared (2.5 - 4.5 um) spectroscopic observations of 34 regions in M 82 including its northern and southern halos. Results. Many of the spectra show strong emission at 3.3 um due to polycyclic aromatic hydrocarbons (PAHs) and relatively weak features at 3.4 - 3.6 um due to aliphatic hydrocarbons. In particular, we clearly detect the PAH 3.3 um emission and the 3.4 - 3.6 um features in halo regions, which are located at a distance of 2 kpc away from the galactic c…
The unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to mixed aromatic/aliphatic organic nanoparticles. More recently, an upper limit of <9% on the aliphatic fraction (i.e., the fraction of carbon atoms in aliphatic form) of the UIE carriers based on the observed intensities of the 3.4 and 3.3 micrometer emission features by attributing them to aliphatic and aromatic C-H stretching modes, respectively, and assuming A_34./A_3.3~0.68 derived from a small se…
Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH3), methylene (>CH2), or diamond-like *CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-f…
Polycyclic Aromatic Hydrocarbon (PAH) molecules have been long adjudged to contribute to the frequently detected distinct emission features at 3.3, 6.2, 7.7, 8.6, 11.2 and 12.7 μm with weaker and blended features distributed in the 3-20 μm region. The comparatively weaker 3.4 μm emission feature has been attributed to have an aliphatic origin as carrier. PAH with aliphatic functional group attached to it is one of the proposed potential candidate carriers for the 3.4 μm emission band, however, the assignment of carrier is still enigmatic. In this work, we employ Density Functional Theory (DFT)…
Superhydrogenated polycyclic aromatic hydrocarbons (PAHs) may be present in H-rich and ultraviolet-poor benign regions. The addition of excess H atoms to PAHs converts the aromatic bonds into aliphatic bonds, the strongest of which falls near 3.4 $μ$m. Therefore, superhydrogenated PAHs are often hypothesized as a carrier of the 3.4 $μ$m emission feature which typically accompanies the stronger 3.3 $μ$m aromatic C--H stretching feature. To assess this hypothesis, we use density function theory to compute the IR vibrational spectra of superhydrogenated PAHs and their ions of various sizes (rangi…
The JWST Proto-PAH project. Computational modeling of the emission carriers
NASA Ames Research Center（美国宇航局艾姆斯研究中心）；SETI Institute（SETI研究所）；Space Telescope Science Institute（太空望远镜科学研究所）；University of North Carolina, Chapel Hill（北卡罗来纳大学教堂山分校）；The University of Western Ontario（韦仕敦大学（西安大略大学））；Cardiff University（卡迪夫大学）；California Institute of Technology（加州理工学院）；ACRI-ST；Centre d’Etudes et de Recherche de Grasse (CERGA)（格拉斯研究与研究中心）
The JWST Proto-PAH project: Aromatic backbones with extensive aliphatic substitution account for both the aromatic and aliphatic emission
The University of Western Ontario（韦仕敦大学）；Institute for Earth and Space Exploration, The University of Western Ontario（韦仕敦大学地球与太空探索研究所）；Space Telescope Science Institute（太空望远镜科学研究所）；University of North Carolina, Chapel Hill（北卡罗来纳大学教堂山分校）；Boston College（波士顿学院）；University of Texas at Austin（德克萨斯大学奥斯汀分校）；Universitat de Barcelona (UB)（巴塞罗那大学）
With the Infrared Camera on board AKARI, we carried out near-infrared (2.5-5.0 micron) spectroscopy of the central kiloparsec region of the barred spiral galaxy, NGC1097, categorized as Seyfert 1 with a circumnuclear starburst ring. Our observations mapped the area of ~50"*10" with the resolution of ~5", covering about a half of the ring and the galactic center. As a result, we spatially resolve the starburst ring in the polycyclic aromatic hydrocarbon 3.3 micron, the aliphatic hydrocarbon 3.4-3.6 micron features, and the hydrogen Br alpha 4.05 micron emission. They exhibit spatial distributio…
The 3.3 $μ$m unidentified infrared emission feature is commonly attributed to C-H stretching band of aromatic molecules. Astronomical observations have shown that this feature is composed of two separate bands at 3.28 and 3.30 $μ$m and the origin of these two bands is unclear. In this paper, we perform vibrational analyses based on quantum mechanical calculations of 153 organic molecules, including both pure aromatic molecules and molecules with mixed aromatic/olefinic/aliphatic hydridizations. We find that many of the C-H stretching vibrational modes in polycyclic aromatic hydrocarbon (PAH) m…
We present insights into the behavior of the astronomical 7.7 $μ$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 $μ$m feature ($λ$7.7). The 7.7 $μ$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…
PAHs constitute a major component of the interstellar medium carbon budget, locking up to 10--20% of the elemental carbon. Sequential fragmentation induced by energetic photons leads to the formation of new species, including fullerenes. However, the exact chemical routes involved in this process remain largely unexplored. In this work, we focus on the first photofragmentation steps, which involve the dehydrogenation of these molecules. For this, we consider a multidisciplinary approach, taking into account the results from experiments, DFT calculations, and modeling using dedicated Monte-Carl…
The JWST will deliver large data sets of high-quality spectral data over the 0.6-28 $μ$m range. It will combine sensitivity, spectral and spatial resolution. Specific tools are required to provide efficient scientific analysis of such large data sets. Our aim is to illustrate the potential of unsupervised learning methods to get insights into chemical variations in the populations that carry the aromatic infrared bands (AIBs), more specifically PAH species and carbonaceous very small grains (VSGs). We present a method based on linear fitting and blind signal separation (BSS) for extracting rep…
The observed large variation in the abundance of deuterium (D) in the interstellar medium (ISM) suggests that a significant fraction of D may be depleted into polycyclic aromatic hydrocarbons (PAHs). Signatures of deuteration of PAHs are expected to appear most clearly through C-D stretching modes at 4.4--4.7 micron, whose strengths in emission spectra relative to those of C-H stretching modes at 3.3--3.5 micron provide the relative abundance of D to hydrogen (H) in PAHs once we have accurate relative band strengths of both stretching modes. We report experimental results of the band strength …
Using a large collection of near-infrared spectra (2.5-5.4 um) of Galactic HII regions and HII region-like objects, we perform a systematic investigation of the astronomical polycyclic aromatic hydrocarbon (PAH) features. 36 objects were observed by the use of the infrared camera onboard the AKARI satellite as a part of a directer's time program. In addition to the well-known 3.3-3.6 um features, most spectra show a relatively-weak emission feature at 5.22 um with sufficient signal-to-noise ratios, which we identify as the PAH 5.25 um band previously reported. By careful analysis, we find good…
Using atomistic simulations, we characterize the adsorption process of organic molecules on carbon nanoparticles, both of which have been reported to be abundant in the interstellar medium (ISM). It is found that the aromatic organics are adsorbed more readily than the aliphatic ones. This selectivity would favor the formation of polycyclic aromatic hydrocarbons (PAHs) or fullerene-like structures in the ISM due to structural similarity. It is also observed in our simulations that the molecules form a monolayer over the nanoparticle surface before stacking up in aggregates. This suggests a pos…
We present a large sample of 2.5-38 $μm$ galaxy spectra drawn from a cross-archival comparison in the AKARI-Spitzer Extragalactic Spectral Survey (ASESS), and investigate a subset of 113 star-forming galaxies with prominent polycyclic aromatic hydrocarbon (PAH) emission spanning a wide range of star formation properties. With AKARI's extended 2.5-5 $μm$ wavelength coverage, we self-consistently model for the first time all PAH emission bands using a modified version of PAHFIT. We find $L_\mathrm{PAH\,3.3}/L_\mathrm{IR}$ $\sim$ 0.1% and the 3.3 $μm$ PAH feature contributes $\sim$1.5-3% to the t…
Growth of Aromatic Hydrocarbon Dust Particles in the Extremely Metal-poor Galaxy Sextans A
Space Telescope Science Institute（太空望远镜科学研究所）；University of California, San Diego（加利福尼亚大学圣地亚哥分校）；University of Toledo（托莱多大学）；Princeton University（普林斯顿大学）；Universiteit Gent（根特大学）；Algoma University（阿尔戈马大学）；The Ohio State University（俄亥俄州立大学）
