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) calculation on a symmetric and compact PAH molecule; coronene (C24H12) with aliphatic side group to investigate any spectral similarities with observed features at 3-4 μm. The side groups considered in this study are -H (hydrogenated), -CH3 (methyl), -CH2-CH3 (ethyl) and -CH=CH2 (vinyl) functional groups. Considering the possible presence of deuterium (D) in PAHs, we also include D in the aliphatic side group to study the spectral behavior. We present a detailed analysis of the IR spectra of these molecules and discuss possible astrophysical implications.
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 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）
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 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…
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,…
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 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…
Here we present the results of an airborne 3-5.4$μ$m spectroscopic study of three young, Carbon-rich planetary nebulae IC 5117, PNG 093.9-00.1, and BD $+$30 3639. These observations were made using the grism spectroscopy mode of the FLITECAM instrument during airborne science operations onboard NASA's Stratospheric Observatory for Infrared Astronomy (SOFIA). The goal of this study is to characterize the 3.3 $μ$m and 5.25 $μ$m PAH dust emission in planetary nebulae and study the evolution of PAH features within evolved stars before their incorporation into new stellar systems in star-forming re…
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 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…
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 intrin…
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…
Aim. We investigate the role of PAHs as a sink for deuterium in the interstellar medium and study UV photolysis as a potential process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologues of D-enriched, protonated anthracene and phenanthrene ions was recorded in a FTICR mass spectrometer. IRMPD spectroscopy using FELIX provided the IR spectra that were compared to DFT vibrational spectra; reaction barriers and rates were also calculated and related to the product abundances. Results. The mass spectra for both UV and I…
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 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 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…
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…
This work reports a 'Density Functional Theory' (DFT) calculation of PAH molecules with a five-member ring to determine the expected region of infrared features. It is highly possible that fullerene molecule might be originated from five-membered ring PAH molecules in the ISM. Effect of ionization and protonation on five-membered ring PAH molecule is also discussed. A detail vibrational analysis of five-membered ring PAH molecule has been reported to further compare with observations and to identify any observational counterpart.
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 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…
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…
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…
This work proposes deuteronated PAH (DPAH+ ) molecules as a potential carrier of the 4.4 and 4.65 μm mid infrared emission bands that have been observationally detected towards the Orion and M17 regions. Density Functional Theory calculations have been carried out on DPAH+ molecules to see the variations in the spectral behaviour from that of a pure PAH. DPAH+ molecules show features that arise due to the stretching of the aliphatic C-D bond. Deuterated PAHs have been previously reported as carriers for such features. However, preferred conditions of ionization of PAHs in the interstellar medi…
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…
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$1.5-3% to the t…
Interstellar Polycyclic Aromatic Hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the ISM. Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a Density Functional Theory (DFT) calculation on dehydrogenated PAH anions to explore t…
Growth of Aromatic Hydrocarbon Dust Particles in the Extremely Metal-poor Galaxy Sextans A
Space Telescope Science Institute（太空望远镜科学研究所）；University of California, San Diego（加利福尼亚大学圣地亚哥分校）；University of Toledo（托莱多大学）；Princeton University（普林斯顿大学）；Universiteit Gent（根特大学）；Algoma University（阿尔戈马大学）；The Ohio State University（俄亥俄州立大学）
PDRs4All XXIII. JWST-MIRI template spectra of PAHs in the Orion Bar obtained with blind signal separation
Institut de Recherche en Astrophysique et Planétologie, Université de Toulouse, Centre National de la Recherche Scientifique (CNRS), Centre National d’Etudes Spatiales（天体物理学与行星学研究所，图卢兹大学，法国国家科学研究中心，法国国家空间研究中心）；NASA Ames Research Center（美国宇航局艾姆斯研究中心）；Centro de Astrobiología (CAB), INTA-CSIC（航空天文学中心（CAB），西班牙国家航空航天技术研究所-西班牙国家研究委员会）；Instituto de Física Fundamental (CSIC)（基础物理研究所（CSIC））；Institut d’Astrophysique Spatiale, Université Paris-Saclay, CNRS（天体物理研究所，巴黎萨克雷大学，法国国家科学研究中心）；Department of Astronomy, Graduate School of Science, The University of Tokyo（东京大学理学研究科天文学系）
The sightline toward the luminous blue hypergiant Cyg OB2-12 is widely used in studying interstellar dust on account of its large extinction ($A_V \simeq 10$ mag) and the fact that this extinction appears to be dominated by dust typical of the diffuse interstellar medium. We present a new analysis of archival ISO-SWS and Spitzer IRS observations of Cyg OB2-12 using a model of the emission from the star and its stellar wind to determine the total extinction $A_λ$ from 2.4--37 $μ$m. In addition to the prominent 9.7 and 18 $μ$m silicate features, we robustly detect absorption features associated …
The 11.2 $μ$m emission band belongs to the family of the `Unidentified' Infrared (UIR) emission bands seen in many astronomical environments. In this work we present a theoretical interpretation of the band characteristics and profile variation for a number of astrophysical sources in which the carriers are subject to a range of physical conditions. The results of Density Functional Theory (DFT) calculations for the solo out-of-plane (OOP) vibrational bending modes of large polycyclic aromatic hydrocarbon (PAH) molecules are used as input for a detailed emission model which includes the temper…
Polycyclic Aromatic Hydrocarbon (PAH) molecules have been long proposed to be a major carrier of 'Unidentified Infrared' (UIR) emission bands that have been observed ubiquitously in various astrophysical environments. These molecules can potentially be an efficient reservoir of deuterium. Once the infrared properties of the deuterium- containing PAHs are well understood both experimentally and theoretically, the interstellar UIR bands can be used as a valuable tool to infer the cause of the deuterium depletion in the ISM. Density Functional Theory (DFT) calculations have been carried out on de…
Small organic molecules are thought to provide building blocks for the formation of complex interstellar polycyclic aromatic hydrocarbons (PAHs). However, the underlying chemical mechanisms remain unclear, particularly concerning the role of interstellar dust. Using molecular dynamics, we simulate the chemical reaction between dehydrogenated benzene molecules in the gas phase or on the surface of an onion-like carbon nanoparticle (NP). The reaction leads to the formation of PAHs of complex structures. The size of the formed molecules is found to roughly increase with increasing temperature up …
This work presents theoretical calculations of infrared spectra of nitrogen (N)-containing polycyclic aromatic hydrocarbon (PAH) molecules with incorporation of N, NH and NH$_2$ using density functional theory (DFT). The properties of their vibrational modes in 2--15 $μ\rm m$ are investigated in relation to the Unidentified Infrared (UIR) bands. It is found that neutral PAHs, when incorporated with NH$_2$ and N (at inner positions), produce intense infrared bands at 6.2, 7.7 and 8.6 $μ\rm m$ that have been normally attributed to ionized PAHs so far. The present results suggest that strong band…
Astronomical evolution mechanism of small size polycyclic aromatic hydrocarbon (PAH) was analyzed using the first principles quantum-chemical calculation. Starting model molecule was benzene (C6H6), which would be transformed to (C5H5) due to carbon void created by interstellar high speed proton attack. In a protoplanetary disk around a young star, molecules would be illuminated by high energy photon and ionized to be cationic-(C5H5). Calculation shows that from neutral to tri-cation, molecule keeps original configuration. At a step of sixth cation, there occurs surprising creation of cyclic-C…
In order to find out capable molecular source of astronomically well observed infrared (IR) spectrum, asymmetric molecular configuration polycyclic aromatic hydrocarbon (PAH) was analyzed by the density functional theory (DFT) analysis. Starting molecules were benzene C6H6, naphthalene C10H8 and 1H-phenalene C13H9. In interstellar space, those molecules will be attacked by high energy photon and proton, which may bring cationic molecules as like C6H6n+ (n=0~3 in calculation), C10H8n+, and C13H9n+, also CH lacked molecules C5H5n+, C9H7n+, and C12H8n+. IR spectra of those molecules were analyzed…
JWST View of the Supernebula in NGC 5253. I. Overview and Continuum Features
UCLA Department of Physics and Astronomy（加州大学洛杉矶分校物理与天文学系）；School of Physics and Astronomy, Tel Aviv University（特拉维夫大学物理与天文学院）；National Radio Astronomy Observatory（美国国家射电天文台）；Department of Astronomy, University of Virginia（弗吉尼亚大学天文学系）；Department of Physics and Astronomy, Chalmers Institute of Technology（查尔姆斯理工大学物理与天文学系）；Academia Sinica Astronomy and Astrophysics（中央研究院天文及天文物理学研究所）；New Mexico Institute of Mining and Technology（新墨西哥矿业与技术学院）
本文利用 JWST 的 MIRI-MRS 研究 NGC 5253 超星云，发现其 HII 区连续谱特征与银河系类似，PAH 特征弱，且超星云核虽消光高但仍有 25%光子逃离。
Modeling a promising carrier of the astronomically observed polycyclic aromatic hydrocarbon (PAH), infrared (IR) spectra of ionized molecules (C9H7) n+ were calculated based on density functional theory (DFT). In a previous study, it was found that void induced coronene C23H12++ could reproduce observed spectra from 3 to 15 micron, which has carbon two pentagons connected with five hexagons. In this paper, we tried to test the simplest model, that is, one pentagon connected with one hexagon, which is indene like molecule (C9H7) n+ (n=0 to 4). DFT based harmonic frequency analysis resulted that…
Protoplanetary disk around a just born young star contains a lot of cosmic dust. especially polycyclic-aromatic-hydrocarbon (PAH), which would become basic component to create biological organics. This study classified many astronomically observed infrared spectra of protoplanetary disks to three typical spectra. Type-A show well known astronomical bands of 6.2, 7.8, 8.6 and 11.3 micrometer. Whereas Type-B included unknown complex bands. Type-(A+B) was their mixed type. We tried to find specific molecule by Density Functional Theory (DFT) calculation. We found that Type-A could be explained by…
