Carbon-rich Circumstellar Envelopes Research Articles

N-Alkanes formed by methyl-methylene addition as a source of meteoritic aliphatics

Aliphatics prevail in asteroids, comets, meteorites and other bodies in our solar system. They are also found in the interstellar and circumstellar media both in gas-phase and in dust grains. Among aliphatics, linear alkanes (n-CnH2n+2) are known to survive in carbonaceous chondrites in hundreds to thousands of parts per billion, encompassing sequences from CH4 to n-C31H64. Despite being systematically detected, the mechanism responsible for their formation in meteorites has yet to be identified. Based on advanced laboratory astrochemistry simulations, we propose a gas-phase synthesis mechanism for n-alkanes starting from carbon and hydrogen under conditions of temperature and pressure that mimic those found in carbon-rich circumstellar envelopes. We characterize the analogs generated in a customized sputter gas aggregation source using a combination of atomically precise scanning tunneling microscopy, non-contact atomic force microscopy and ex-situ gas chromatography-mass spectrometry. Within the formed carbon nanostructures, we identify the presence of n-alkanes with sizes ranging from n-C8H18 to n-C32H66. Ab-initio calculations of formation free energies, kinetic barriers, and kinetic chemical network modelling lead us to propose a gas-phase growth mechanism for the formation of large n-alkanes based on methyl-methylene addition (MMA). In this process, methylene serves as both a reagent and a catalyst for carbon chain growth. Our study provides evidence of an aliphatic gas-phase synthesis mechanism around evolved stars and provides a potential explanation for its presence in interstellar dust and meteorites.

Energetic and Spectroscopic Properties of Astrophysically Relevant MgC4H Radicals Using High-Level Ab Initio Calculations.

Considering the importance of magnesium-bearing hydrocarbon molecules (MgCnH; n = 2, 4, and 6) in the carbon-rich circumstellar envelopes (e.g., IRC+10216), a total of 28 constitutional isomers of MgC4H have been theoretically investigated using density functional theory (DFT) and coupled-cluster methods. The zero-point vibrational energy corrected relative energies at the ROCCSD(T)/cc-pCVTZ level of theory reveal that the linear isomer, 1-magnesapent-2,4-diyn-1-yl (1, 2Σ+), is the global minimum geometry on the MgC4H potential energy surface. The latter has been detected both in the laboratory and in the evolved carbon star, IRC+10216. The calculated spectroscopic data for 1 match well with the experimental observations (error ∼ 0.78%) which validates our theoretical methodology. Plausible isomerization processes happening among different isomers are examined using DFT and coupled-cluster methods. CASPT2 calculations have been performed for a few isomers exhibiting multireference characteristics. The second most stable isomer, 1-ethynyl-1λ3-magnesacycloprop-2-ene-2,3-diyl (2, 2A1, μ = 2.54 D), is 146 kJ mol-1 higher in energy than 1 and possibly the next promising candidate to be detected in the laboratory or in the interstellar medium in future.

A 3 mm molecular line survey toward the C-star envelope CIT 6

Abstract We present an unbiased molecular line survey toward the carbon-rich circumstellar envelope CIT 6 carried out between 90 and 116 GHz with the Arizona Radio Observatory 12 m telescope. A total of 42 lines assigned to 10 molecular species and four isotopologues are detected. Despite the absence of any newly identified circumstellar molecules, several transitions are freshly reported for this object. This work is a complement to our previous line survey toward CIT 6 in the frequency ranges of 36–49 GHz and 131–268 GHz. Based on the measurements and in combination with previously published data, we perform a rotation-diagram analysis to determine the column densities, excitation temperatures, and fractional abundances of the molecules. The excitation temperature varies along the radius. The abundance pattern of CIT 6 is broadly consistent with that of the prototype C-star IRC +10216 at the specified detection sensitivity, indicating that the molecular richness in IRC +10216 cannot be attributed to an interpretation of unusual chemistry. Nevertheless, subtle distinctions between the two C-stars are found. The higher abundance of carbon-chain molecules and lower 12C$/$13C ratio in CIT 6 compared to IRC +10216 imply that the former is more massive or in a more evolved phase than the latter.

Grain Alignment in the Circumstellar Shell of IRC+10° 216

Dust-induced polarization in the interstellar medium (ISM) is due to asymmetric grains aligned with an external reference direction, usually the magnetic field. For both the leading alignment theories, the alignment of the grain’s angular momentum with one of its principal axes and the coupling with the magnetic field requires the grain to be paramagnetic. Of the two main components of interstellar dust, silicates are paramagnetic, while carbon dust is diamagnetic. Hence, carbon grains are not expected to align in the ISM. To probe the physics of carbon grain alignment, we have acquired Stratospheric Observatory for Infrared Astronomy/Higch-resolution Airborne Wideband Camera-plus far-infrared photometry and polarimetry of the carbon-rich circumstellar envelope (CSE) of the asymptotic giant branch star IRC+10° 216. The dust in such CSEs are fully carbonaceous and thus provide unique laboratories for probing carbon grain alignment. We find a centrosymmetric, radial, polarization pattern, where the polarization fraction is well correlated with the dust temperature. Together with estimates of a low fractional polarization from optical polarization of background stars, we interpret these results to be due to a second-order, direct radiative external alignment of grains without internal alignment. Our results indicate that (pure) carbon dust does not contribute significantly to the observed ISM polarization, consistent with the nondetection of polarization in the 3.4 μm feature due to aliphatic CH bonds on the grain surface.

Hydroaluminum Isocyanide Isomers: Prediction of Spectroscopic Properties

Abstract Metal cyanides and isocyanides play a relevant role in the metal chemistry of the carbon-rich circumstellar envelope IRC+10216. It is thought that hydrometal cyanides/isocyanides could also be present in these environments; in fact, HMgNC has been detected in the same source that MgCN, MgNC, and AlNC. The aim of this work is to provide information about hydroaluminum cyanide/isocyanide. For this goal, a comprehensive analysis of the doublet and quartet potential energy surfaces of the [Al, C, H, N] system has been carried out. Different quantum chemistry methodologies from density functional theory to ab initio have been employed. For the [Al, C, H, N] isomers, the stability against dissociation and their interconversion processes have been analyzed. Our results show that the most relevant isomers from an experimental point of view are HAlCN and HAlNC. HAlNC has been found to be the most stable isomer followed by HAlCN, which is located at 1.59 kcal mol−1 (0.0689 eV) at the composite level. The interconversion process between HAlCN and HAlNC presents an energy barrier of 10.0 kcal mol−1 (5032 K) that makes this process not viable in the interstellar medium. We provide a complete set of relevant spectroscopic parameters for rotational spectroscopy for both HAlCN and HAlNC isomers using state-of-the-art quantum chemical computations, mandatory to guide an eventual laboratory or interstellar detection. Moreover, both isomers present sizable μ a dipole moment components (3.7 and 3.3 D, respectively), which are large enough to enable a characterization by means of rotational spectroscopy, further increasing their interest as interstellar candidates.

The Fundamental Vibrational Frequencies and Spectroscopic Constants of the Dicyanoamine Anion, NCNCN− (C2N3 −): Quantum Chemical Analysis for Astrophysical and Planetary Environments

Abstract Detecting anions in space has relied on a strong collaboration between theoretical and laboratory analyses to measure rotational spectra and spectroscopic constants to high accuracy. The advent of improved quantum chemical tools operating at higher accuracy and reduced computational cost is a crucial solution for the fundamental characterization of astrophysically relevant anions and their detection in the interstellar medium (ISM) and planetary atmospheres. In this context, we have turned toward the quantum chemical analysis of the penta-atomic dicyanoamine anion NCNCN− ( ), a structurally bent and polar compound. We have performed high-level coupled cluster theory quartic force field computations of satisfying both computational cost and accuracy conditions. We provide for the first time accurate spectroscopic constants and vibrational frequencies for this ion. In addition to exhibiting various Fermi resonances, displays a bright ν 2 (2130.9 cm−1) and a less intense ν 1 (2190.7 cm−1) fundamental vibrational frequency, making for strong markers for future infrared observations <5 μm. We have also determined near-IR overtone and combination bands of the bright fundamentals for which the 2ν 2 at 4312.1 cm−1 (2.319 μm) is the best candidate. could potentially exist and be detected in nitrogen-rich environments of the ISM such as IRC +10216 and other carbon-rich circumstellar envelopes, or in the atmosphere of Saturn’s moon Titan, where advanced N-based reactions may lead to its formation.

A Combined Experimental and Theoretical Study on the Formation of the 2-Methyl-1-silacycloprop-2-enylidene Molecule via the Crossed Beam Reactions of the Silylidyne Radical (SiH; X(2)Π) with Methylacetylene (CH3CCH; X(1)A1) and D4-Methylacetylene (CD3CCD; X(1)A1).

The bimolecular gas-phase reactions of the ground-state silylidyne radical (SiH; X(2)Π) with methylacetylene (CH3CCH; X(1)A1) and D4-methylacetylene (CD3CCD; X(1)A1) were explored at collision energies of 30 kJ mol(-1) under single-collision conditions exploiting the crossed molecular beam technique and complemented by electronic structure calculations. These studies reveal that the reactions follow indirect scattering dynamics, have no entrance barriers, and are initiated by the addition of the silylidyne radical to the carbon-carbon triple bond of the methylacetylene molecule either to one carbon atom (C1; [i1]/[i2]) or to both carbon atoms concurrently (C1-C2; [i3]). The collision complexes [i1]/[i2] eventually isomerize via ring-closure to the c-SiC3H5 doublet radical intermediate [i3], which is identified as the decomposing reaction intermediate. The hydrogen atom is emitted almost perpendicularly to the rotational plane of the fragmenting complex resulting in a sideways scattering dynamics with the reaction being overall exoergic by -12 ± 11 kJ mol(-1) (experimental) and -1 ± 3 kJ mol(-1) (computational) to form the cyclic 2-methyl-1-silacycloprop-2-enylidene molecule (c-SiC3H4; p1). In line with computational data, experiments of silylidyne with D4-methylacetylene (CD3CCD; X(1)A1) depict that the hydrogen is emitted solely from the silylidyne moiety but not from methylacetylene. The dynamics are compared to those of the related D1-silylidyne (SiD; X(2)Π)-acetylene (HCCH; X(1)Σg(+)) reaction studied previously in our group, and from there, we discovered that the methyl group acts primarily as a spectator in the title reaction. The formation of 2-methyl-1-silacycloprop-2-enylidene under single-collision conditions via a bimolecular gas-phase reaction augments our knowledge of the hitherto poorly understood silylidyne (SiH; X(2)Π) radical reactions with small hydrocarbon molecules leading to the synthesis of organosilicon molecules in cold molecular clouds and in carbon-rich circumstellar envelopes.

On the formation of pyridine in the interstellar medium.

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block - the aromatic pyridine molecule - has remained elusive for decades. Here we reveal a potential pathway to a facile pyridine (C5H5N) synthesis via the reaction of the cyano vinyl (C2H2CN) radical with vinyl cyanide (C2H3CN) in high temperature environments simulating conditions in carbon-rich circumstellar envelopes of Asymptotic Giant Branch (AGB) stars like IRC+10216. Since this reaction is barrier-less, pyridine can also be synthesized via this bimolecular reaction in cold molecular clouds such as in TMC-1. The synchronized aromatization of precursors readily available in the interstellar medium leading to nitrogen incorporation into the aromatic rings would open up a novel route to pyridine derivatives such as vitamin B3 and pyrimidine bases as detected in carbonaceous chondrites like Murchison.

Small carbon chains in circumstellar envelopes

Observations were made for a number of carbon-rich circumstellar envelopes using the Phoenix spectrograph on the Gemini South telescope to determine the abundance of small carbon chain molecules. Vibration-rotation lines of the $\nu_{3}$ antisymmetric stretch of C$_{3}$ near 2040 cm$^{-1}$ (4.902 $\mu$m) have been used to determine the column density for four carbon-rich circumstellar envelopes: CRL 865, CRL 1922, CRL 2023 and IRC +10216. We additionally calculate the column density of C$_{5}$ for IRC +10216, and provide an upper limit for 5 more objects. An upper limit estimate for the C$_{7}$ column density is also provided for IRC+10216. A comparison of these column densities suggest a revision to current circumstellar chemical models may be needed.

HERSCHEL /HIFI SEARCH FOR H$_2^{17}$O AND H$_2^{18}$O IN IRC+10216: CONSTRAINTS ON MODELS FOR THE ORIGIN OF WATER VAPOR

We report the results of a sensitive search for the minor isotopologues of water, H2-17O and H2-18O, toward the carbon-rich AGB star IRC+10216 (a.k.a. CW Leonis) using the HIFI instrument on the Herschel Space Observatory. This search was motivated by the fact that any detection of isotopic enhancement in the H2-17O and H2-18O abundances would have strongly implicated CO photodissociation as the source of the atomic oxygen needed to produce water in a carbon-rich circumstellar envelope. Our observations place an upper limit of 1/470 on the H2-17O/H2-16O abundance ratio. Given the isotopic 17O/16O ratio of 1/840 inferred previously for the photosphere of IRC+10216, this result places an upper limit of a factor 1.8 on the extent of any isotope-selective enhancement of H2-17O in the circumstellar material, and provides an important constraint on any model that invokes CO photodissociation as the source of O for H2O production. In the context of the clumpy photodissociation model proposed previously for the origin of water in IRC+10216, our limit implies that 12C-16O (not 13C-16O or SiO) must be the dominant source of 16O for H2O production, and that the effects of self-shielding can only have reduced the 12C-16O photodissociation rate by at most a factor ~ 2.

The UMIST database for astrochemistry 2012

We present the fifth release of the UMIST Database for Astrochemistry (UDfA). The new reaction network contains 6173 gas-phase reactions, involving 467 species, 47 of which are new to this release. We have updated rate coefficients across all reaction types. We have included 1171 new anion reactions and updated and reviewed all photorates. In addition to the usual reaction network, we also now include, for download, state-specific deuterated rate coefficients, deuterium exchange reactions and a list of surface binding energies for many neutral species. Where possible, we have referenced the original source of all new and existing data. We have tested the main reaction network using a dark cloud model and a carbon-rich circumstellar envelope model. We present and briefly discuss the results of these models.

MOLECULAR LINE OBSERVATIONS OF THE CARBON-RICH CIRCUMSTELLAR ENVELOPE CIT 6 AT 7 mm WAVELENGTHS

We present a {lambda}7 mm spectral line survey of the carbon-rich circumstellar envelope (CSE) CIT 6 using the 45 m telescope at the Nobeyama Radio Observatory. A total of 25 spectral features belonging to five molecular species (HC{sub 3}N, HC{sub 5}N, HC{sub 7}N, SiO, and CS) are detected, enabling us to investigate the chemistry of cyanopolyyne chains. The line strengths are compared with those of the proto-typical carbon-rich CSE IRC+10216. The results show that the cyanopolyyne molecules are enhanced in CIT 6, suggesting that it is more evolved than IRC+10216. In order to investigate the structure of CIT 6, we have constructed a three-dimensional spatiokinematic model. By comparing the observed line profiles with the models, we conclude that this envelope is asymmetric and is composed of several incomplete shells.

A PILOT IMAGING LINE SURVEY OF RW LMi AND IK Tau USING THE EXPANDED VERY LARGE ARRAY

We report on a pilot imaging line survey (36.0 - 37.0 GHz, with ~1 km/s spectral channels) with the Expanded Very Large Array for two asymptotic giant branch stars, RW LMi (= CIT6, which has a carbon-rich circumstellar envelope) and IK Tau (= NML Tau, with an oxygen-rich circumstellar envelope). Radio continuum emission consistent with photospheric emission was detected from both stars. From RW LMi we imaged the HC3N (J = 4 -> 3) emission. The images show several partial rings of emission; these multiple shells trace the evolution of the CSE from 400 to 1200 years. SiS (J = 2 -> 1) emission was detected from both RW LMi and IK Tau. For both stars the SiS emission is centrally condensed with the peak line emission coincident with the stellar radio continuum emission. In addition, we have detected weak HC7N (J = 32 -> 31) emission from RW LMi.

COMPARATIVE SPECTRA OF OXYGEN-RICH VERSUS CARBON-RICH CIRCUMSTELLAR SHELLS: VY CANIS MAJORIS AND IRC +10216 AT 215-285 GHz

A sensitive (1{\sigma} rms at 1 MHz resolution ~3 mK) 1 mm spectral line survey (214.5-285.5 GHz) of VY Canis Majoris (VY CMa) and IRC+10216 has been conducted to compare the chemistries of oxygen and carbon-rich circumstellar envelopes. This study was carried out using the Submillimeter Telescope (SMT) of the Arizona Radio Observatory (ARO) with a new ALMA-type receiver. This survey is the first to chemically characterize an O-rich circumstellar shell at millimeter wavelengths. In VY CMa, 128 emission features were detected arising from 18 different molecules, and in IRC+10216, 720 lines were observed, assigned to 32 different species. The 1 mm spectrum of VY CMa is dominated by SO2 and SiS; in IRC +10216, C4H and SiC2 are the most recurrent species. Ten molecules were common to both sources: CO, SiS, SiO, CS, CN, HCN, HNC, NaCl, PN, and HCO+. Sulfur plays an important role in VY CMa, but saturated/unsaturated carbon dominates the molecular content of IRC+10216, producing CH2NH, for example. Although the molecular complexity of IRC+10216 is greater, VY CMa supports a unique "inorganic" chemistry leading to the oxides PO, AlO, and AlOH. Only diatomic and triatomic compounds were observed in VY CMa, while species with 4 or more atoms are common in IRC+10216, reflecting carbon's ability to form strong multiple bonds, unlike oxygen. In VY CMa, a new water maser (v_2=2) has been found, as well as vibrationally-excited NaCl. Toward IRC+10216, vibrationally-excited CCH was detected for the first time.

Gas phase atomic metals in the circumstellar envelope of IRC+10216

We report the results of a search for gas phase atomic metals in the circumstellar envelope of the asymptotic giant branch carbon star IRC+10216. The search was made using high resolution (<i>λ<i/>/<i>Δ<i/> <i>λ<i/> = 50 000) optical absorption spectroscopy of a background star that probes the envelope on a line of sight 35´´ from the center. The metal species that we detect in the envelope include , , , , , and , with upper limits for , , , , and . The observations are used to determine the metal abundances in the gas phase and the condensation onto grains. The metal depletions in the envelope range from a factor of 5 for Na to 300 for Ca, with some similarity to the depletion pattern in interstellar clouds. Our results directly constrain the condensation efficiency of metals in a carbon-rich circumstellar envelope and the mix of solid and gas phase metals returned by the star to the interstellar medium. The abundances of the uncondensed metal atoms that we observe are typically larger than the abundances of the metal-bearing molecules detected in the envelope. The metal atoms are therefore the major metal species in the gas phase and likely play a key role in the metal chemistry.

DENSITY-ENHANCED GAS AND DUST SHELLS IN A NEW CHEMICAL MODEL FOR IRC+10216

A new chemical model is presented for the carbon-rich circumstellar envelope (CSE) of the asymptotic giant branch star IRC+10216. The model includes shells of matter with densities that are enhanced relative to the surrounding circumstellar medium. The chemical model uses an updated reaction network including reactions from the RATE06 database and a more detailed anion chemistry. In particular, new mechanisms are considered for the formation of CN{sup -}, C{sub 3}N{sup -}, and C{sub 2}H{sup -}, and for the reactions of hydrocarbon anions with atomic nitrogen and with the most abundant cations in the CSE. New reactions involving H{sup -} are included which result in the production of significant amounts of C{sub 2}H{sup -} and CN{sup -} in the inner envelope. The calculated radial molecular abundance profiles for the hydrocarbons C{sub 2}H, C{sub 4}H, and C{sub 6}H and the cyanopolyynes HC{sub 3}N and HC{sub 5}N show narrow peaks which are in better agreement with observations than previous models. Thus, the narrow rings observed in molecular microwave emission surrounding IRC+10216 are interpreted as arising in regions of the envelope where the gas and dust densities are greater than the surrounding circumstellar medium. Our models show that CN{sup -} and C{sub 2}H{sup -}more » may be detectable in IRC+10216 despite the very low theorized radiative electron attachment rates of their parent neutral species. We also show that magnesium isocyanide (MgNC) can be formed in the outer envelope through radiative association involving Mg{sup +} and the cyanopolyyne species.« less

Molecular Shells in IRC+10216: Evidence for Nonisotropic and Episodic Mass‐Loss Enhancement

We report high angular resolution VLA observations of cyanopolyyne molecules HC3N and HC5N from the carbon rich circumstellar envelope of IRC+10216. The observed low-lying rotational transitions trace a much more extended emitting region than seen in previous observations at higher frequency transitions. We resolve the hollow quasi-spherical distribution of the molecular emissions into a number of clumpy shells. These molecular shells coincide spatially with dust arcs seen in deep optical images of the IRC+10216 envelope, allowing us to study for the first time the kinematics of these features. We find that the molecular and dust shells represent the same density enhancements in the envelope separated in time by ~120 to ~360 yr. From the angular size and velocity spread of the shells, we estimate that each shell typically covers about 10% of the stellar surface at the time of ejection. The distribution of the shells seems to be random in space. The good spatial correspondence between HC3N and HC5N emissions is in qualitative agreement with a recent chemical model that takes into account the presence of density-enhanced shells. The broad spatial distribution of the cyanopolyyne molecules, however, would necessitate further study on their formation.

On Silicon Carbide Grains as the Carrier of the 21 μm Emission Feature in Post-Asymptotic Giant Branch Stars

The mysterious 21 μm emission feature seen in 12 proto-planetary nebulae remains unidentified since its first detection in 1989. Over a dozen candidate materials have been proposed within the past decade, but none of them have received general acceptance. Very recently, silicon carbide (SiC) grains with impurities were suggested to be the carrier of this enigmatic feature, based on recent laboratory data that doped SiC grains exhibit a resonance at ~21 μm. This proposal gains strength from the fact that SiC is a common dust species in carbon-rich circumstellar envelopes. However, SiC dust has a strong vibrational band at ~11.3 μm. We show in this Letter that in order to be consistent with the observed flux ratios of the 11.3 μm feature to the 21 μm feature, the band strength of the 21 μm resonance has to be very strong, too strong to be consistent with current laboratory measurements. But this does not yet readily rule out the SiC hypothesis since recent experimental results have demonstrated that the 21 μm resonance of doped SiC becomes stronger as the C impurity increases. Further laboratory measurements of SiC dust with high fractions of C impurity are urgently needed to test the hypothesis of SiC as the carrier of the 21 μm feature.

A crossed beam and ab initio study of the C 2(X 1Σ g+ /a 3∏ u) + C 2H 2(X 1Σ g+) reactions

The reaction dynamics of C 2 in the ground ( 1Σ g +) and first electronically excited ( 3∏ u) states with the simplest alkyne, acetylene C 2H 2(X 1Σ g +), were investigated in a crossed molecular beam setup at a nominal collision energy of 24.1 kJ mol −1. The experimental data expose the existence of a C 2/H exchange pathway to form C 4H + H. The experimental results were combined with electronic structure calculations on the singlet and triplet C 4H 2 surfaces. The reaction of C 2(X 1Σ g +) was found to proceed via indirect scattering dynamics through addition of C 2 to the carbon–carbon triple bond. On the triplet surface, C 2(a 3∏ u) adds also to the acetylenic triple bond. Dominated by large impact parameters, this process favors the formation of two short lived chain-like triplet C 4H 2 isomers. For both reactions, the identification of the butadiynyl radical as a relevant product presents an important step to refine the networks of reactions for the modeling of polycyclic aromatic hydrocarbons formation together with that of their hydrogen deficient precursors in the interstellar medium, in carbon-rich circumstellar envelopes and pre-planetary nebula, and in combustion flames.

Circumstellar dust shells around long-period variables

The existence of warm zones of an enhanced molecular content surrounding the photospheres of AGB stars has been postulated to explain observed molecular absorption/emission components which are in excess of the results obtained from classical hydrostatic model atmospheres. We have analyzed the chemical equilibrium molecular composition of time-dependent models of carbon-rich circumstellar envelopes for various combinations of the stellar parameters and found that groups of molecules appear to be present in different zones with temporally varying temperature and density. The regions of enhanced molecular abundances are situated between the stellar photosphere and the circumstellar dust shell. In the models, these zones are produced by the levitation of the atmospheric gas due to the dissipation of shock waves and/or due to radiation pressure on molecules and dust.