In the interstellar medium, carbon is distributed between the gas and solid phases. However, while about half of the expected carbon abundance can be accounted for in the gas phase, there is considerable uncertainty as to the amount incorporated in interstellar dust.
The aliphatic component of the carbonaceous dust is of particular interest because it produces a significant 3.4 $μ$m absorption feature when viewed against a background radiation source. The optical depth of the 3.4 $μ$m absorption feature is related to the number of aliphatic carbon C-H bonds along the line of sight. It is possible to estimate the column density of carbon locked up in the aliphatic hydrocarbon component of interstellar dust from quantitative analysis of the 3.4 $μ$m interstellar absorption feature providing that the absorption coefficient of aliphatic hydrocarbons incorporated in the interstellar dust is known.
We generated laboratory analogues of interstellar dust by experimentally mimicking interstellar/circumstellar conditions. The resultant spectra of these dust analogues closely match those from astronomical observations. The measurements of the absorption coefficient of aliphatic hydrocarbons incorporated in the analogues were carried out by a procedure which combined FTIR and $^{13}$C NMR spectroscopies. The absorption coefficients obtained for both interstellar analogues were found to be in close agreement (4.76(8) $\times$ 10$^{-18}$ cm group$^{-1}$ and 4.69(14) $\times$ 10$^{-18}$ cm group$^{-1}$), less than half those obtained in studies using small aliphatic molecules. The results thus obtained permit direct calibration of the astronomical observations, providing rigorous estimates of the amount of aliphatic carbon in the interstellar medium.
We implement a new observational method for mapping the aliphatic hydrocarbon content in the solid phase in our Galaxy, based on spectrophotometric imaging of the 3.4 $μ$m absorption feature from interstellar dust. We previously demonstrated this method in a field including the Galactic Centre cluster. We applied the method to a new field in the Galactic centre where the 3.4 $μ$m absorption feature has not been previously measured and we extended the measurements to a field in the Galactic plane to sample the diffuse local interstellar medium, where the 3.4 $μ$m absorption feature has been pre…
In the interstellar medium, the cosmic elemental carbon abundance includes the total carbon in both gas and solid phases. The aim of the study was to trial a new method for measuring the amount and distribution of aliphatic carbon within interstellar dust over wide fields of view of our Galaxy. This method is based on measurement of the 3.4 $μ$m absorption feature from aliphatic carbonaceous matter. This can readily be achieved for single sources using IR spectrometers. However, making such measurements over wide fields requires an imaging IR camera, equipped with narrow-band filters that are …
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 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 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…
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 $μ$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…
While it is well recognized that interstellar grains are made of amorphous silicates and some form of carbonaceous materials, it remains debated regarding what exact chemical and physical form the carbonaceous component takes. Contemporary grain models assume that the silicate and carbon components are either physically separated, or they form a core-mantle structure, or they agglomerate to form porous composites. The core-mantle model posits that the mantle is made of some sort of aliphatic hydrocarbon materials and is responsible for the 3.4 micrometer absorption feature ubiquitously seen in…
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 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…
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…
In the interstellar medium, carbon (nano-)grains are a major component of interstellar dust. This solid phase is more vulnerable to processing and destruction than its silicate counterpart. It exhibits a complex, size-dependent evolution due to interactions within different radiative and dynamical environments. Infrared signatures of these nanocarbon grains are seen in a large number of disks around Herbig HAeBe stars. We probe the composition and evolution of carbon nano-grains at the surface of (pre-)transitional protoplanetary disks around Herbig stars. We present spatially resolved infrare…
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)…
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…
School of Astronomy & Space Science, Nanjing University（南京大学天文与空间科学学院）；Institute for Astronomy, University of Hawaii（夏威夷大学天体物理研究所）；Key Laboratory of Modern Astronomy and Astrophysics, Nanjing University, Ministry of Education（南京大学现代天文与天体物理教育部重点实验室）
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…
Supervised machine learning models are trained with various molecular descriptors to predict infrared emission spectra of interstellar polycyclic aromatic hydrocarbons. We demonstrate that a feature importance analysis based on the random forest algorithm can be utilized to explore the physical correlation between emission features. Astronomical correlations between infrared bands are analyzed as examples of demonstration by finding the common molecular fragments responsible for different bands, which improves the current understanding of the long-observed correlations. We propose a way to qua…
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 …
Gas-phase and solid-state chemistry in low-temperature interstellar clouds and cores leads to a D/H enhancement in interstellar ices, which is eventually inherited by comets, meteorites, and even planetary satellites. Hence, the D/ H ratio has been widely used as a tracer for the origins of extraterrestrial chemistry. However, the D/H ratio can also be influenced by cosmic rays, which are ubiquitous and can penetrate even dense interstellar molecular cores. The effects of such high-energy radiation on deuterium fractionation have not been studied in a quantitative manner. In this study, we pre…
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…
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）
Ubiquitous unidentified infrared emission bands are seen in many astronomical sources. Although these bands are widely, if not unanimously, attributed to the collective emission from polycyclic aromatic hydrocarbons, no single species from this class has been detected in space. We present the discovery of two -CN functionalized polycyclic aromatic hydrocarbons, 1- and 2-cyanonaphthalene, in the interstellar medium aided by spectral matched filtering. Using radio observations with the Green Bank Telescope, we observe both bi-cyclic ring molecules in the molecular cloud TMC-1. We discuss potenti…
We design and train a neural network (NN) model to efficiently predict the infrared spectra of interstellar polycyclic aromatic hydrocarbons (PAHs) with a computational cost many orders of magnitude lower than what a first-principles calculation would demand. The input to the NN is based on the Morgan fingerprints extracted from the skeletal formulas of the molecules and does not require precise geometrical information such as interatomic distances. The model shows excellent predictive skill for out-of-sample inputs, making it suitable for improving the mixture models currently used for unders…
We examine the annihilation of positrons on polycyclic aromatic hydrocarbon (PAH) molecules in interstellar medium conditions. We estimate the annihilation rates of positrons on PAHs by a semi-empirical approach. We show that PAHs can play a significant role in the overall galactic positron annihilation picture and use the annihilation rates and INTEGRAL galactic emission measurements to constrain the amount of PAHs present in the ISM. We find an upper limit of 4.6 x 10^-7 for the PAH abundance.
Interstellar dust shows ubiquitous interstellar infrared spectrum (IR) due to polycyclic aromatic hydrocarbon (PAH). By our previous quantum chemistry calculation, it was suggested that a molecule group having hydrocarbon pentagon-hexagon combined skeleton could reproduce observed IR of dust clouds in Milky Way galaxy. This paper extends to other many galaxies. Typical galaxies are NGC6946 and M83. Those infrared spectrum were compared with that of a model molecule (C23H12)2+ having hydrocarbon two pentagons combined with five hexagons. Observed major infrared bands of 6.2, 7.7, 8.6, and 11.3 …
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…
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）
Hydrocarbons are ubiquitous in the interstellar medium, observed in diverse environments ranging from diffuse to molecular dark clouds and strong photon-dominated regions near HII regions. Recently, two broad diffuse interstellar bands (DIBs) at 4881Å and 5450Å were attributed to the linear version of propynylidene l-C3H2, a species whose more stable cyclic conformer c-C3H2 has been widely observed in the diffuse interstellar medium at radio wavelengths. This attribution has already been criticized on the basis of indirect plausibility arguments because the required column densities are quite …
The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelératéur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In…
The present study provides an investigation on the deposition of carbon-related products on different substrates using a high power dielectric barrier discharge fed with helium and saturated hydrocarbon gases. The discharge has been characterized by means of voltage-current measurements, while the neutral species and the dissociation compounds accumulated in the plasma reactor have been analyzed by Fourier-transform infrared (FTIR) spectroscopy. The properties of non-aromatic hydrogenated amorphous carbon (a-C:H) films and 'fluffy' carbon dust deposited onto various substrates are analyzed by …
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 …
Polycyclic Aromatic Hydrocarbons (PAHs) are considered as a major constituent of interstellar dust. They have been proposed as the carriers of the Aromatic Infrared Bands (AIBs) observed in emission in the mid-IR. They likely have a significant contribution to various features of the extinction curve such as the 220 nm bump,the far-UV rise and the diffuse interstellar bands. Emission bands are also expected in the far-IR, which are better fingerprints of molecular identity than the AIBs. They will be searched for with the Herschel Space Observatory. Rotational emission is also expected in the …
The work is devoted to the adaptation of the results of laboratory studies of the laser-induced dissociation of molecules of benzene adsorbed on a quartz substrate to the conditions of the interstellar medium. Adsorption was performed under conditions of low temperature and deep vacuum. The difference between the photolysis of adsorbed molecules and molecules in the gas phase is identified. Significance of process of photolytic desorption in the interstellar conditions is analyzed, in particular, in the conditions of photodissociation regions. It is shown that the efficiency and dissociation c…
Reflection Nebula NGC2023 shows specific interstellar infrared spectrum due to polycyclic aromatic hydrocarbon (PAH) in a wide wavelength range from 5 to 20 micrometer. By our previous quantum chemistry calculation, it was suggested that a molecule group having hydrocarbon pentagon-hexagon combined skeleton could reproduce ubiquitous interstellar infrared spectrum. In this paper, observed NGC2023 spectrum was compared in detail with such carrier candidates. First model molecule was di-cation (C23H12)2+ with two hydrocarbon pentagons combined with five hexagons. Observed strong infrared bands w…
We report the results of a search for emission features from interstellar deuterated polycyclic aromatic hydrocarbons (PAHs) in the 4um region with the Infrared Camera (IRC) onboard AKARI. No significant excess emission is seen in 4.3-4.7um in the spectra toward the Orion Bar and M17 after the subtraction of line emission from the ionized gas. A small excess of emission remains at around 4.4 and 4.65um, but the ratio of their intensity to that of the band emission from PAHs at 3.3-3.5um is estimated as 2-3%. This is an order of magnitude smaller than the values previously reported and also tho…
In order to find out capable chemical evolution step from astronomically created organic in interstellar space to biological organic on the earth, infrared spectrum of nitrogen substituted carbon pentagon-hexagon coupled polycyclic aromatic hydrocarbon was analyzed by the density functional theory. Ionization was modeled from neutral to tri-cation. Among one nitrogen and two nitrogen substituted NPAH, we could find good examples showing similar IR behavior with astronomically well observed one as like C8H6N1, C7H5N2, and C7H5N2. We can imagine that such ionized NPAH may be created in interstel…
Observations of diffuse clouds showed that they contain a number of simple hydrocarbons (e.g. CH, C$_2$H, (l- and c-)C$_3$H$_2$, and C$_4$H) in abundances that may be difficult to understand on the basis of conventional gas-phase chemical models. Recent experimental results revealed that the photo-decomposition mechanism of hydrogenated amorphous carbon (HAC) and of solid hexane releases a range of hydrocarbons into the gas, containing up to 6 C-atoms for the case of HAC decomposition. These findings motivated us to introduce a new potential input to interstellar chemistry; the "top-down" or d…
A model of key processes influencing the evolution of a hydrocarbon grain of an arbitrary size under astrophysical conditions corresponding to ionized hydrogen regions (HII regions) and supernova remnants is presented. The considered processes include aromatization and photodestruction, sputtering by electrons and ions, and shattering due to collisions between grains. The model can be used to simulate the grain size distribution and the aromatization degree during the evolution of HII regions and supernova remnants for a specified radiation field, relative velocity of gas and dust, etc. The co…
The aim of this work is to link the broad lambda 5450 diffuse interstellar band (DIB) to a laboratory spectrum recorded through an expanding acetylene plasma. Cavity ring-down direct absorption spectra and astronomical observations of HD 183143 with the HERMES spectrograph on the Mercator Telescope in La Palma and the McKellar spectrograph on the DAO 1.2 m Telescope are compared. In the 543-547 nm region a broad band is measured with a band maximum at 545 nm and FWHM of 1.03(0.1) nm coinciding with a well-known diffuse interstellar band at lambda 5450 with FWHM of 0.953 nm. A coincidence is fo…
By applying quantum chemical calculation, interstellar infrared spectrum was categorized to three classes. Type-A show unusual feature of strong peaks at 11.3,12.9, and 14.0 micrometer. Usually observed 6.2, 7.7, and 8.6 micrometer bands are weak or not recognized. Typical examples are NGC1316 and NGC4589. Such spectrum could be identified for the first time by pure carbon molecule (C23)2+ (dication) having two carbon pentagons combined with five hexagons. Calculated spectrum coincided well at 11.3, 13.0, and 14.0 micrometer. Also we could find more coincidence at 5.2, 5.6, 7.6, 8.8,10.6,15.7 …
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…
Aims. Due to the limitations of current computational technology, the fragmentation and isomerization products of vibrationally-excited polycyclic aromatic hydrocarbon (PAH) molecules and their derivatives are poorly studied. In this work, we investigate the intermediate products of PAHs and their derivatives as well as the gas-phase reactions relevant to the interstellar medium, with coronene as a case study. Methods. Based on the semi-empirical method of PM3 as implemented in the CP2K program, molecular dynamics simulations are performed to model the major processes (e.g., vibrations, fragme…
