Of the over 150 different molecular species detected in the interstellar and circumstellar media, approximately 50 contain 6 or more atoms. These molecules, labeled complex by astronomers if not by chemists, all contain the element carbon and so can be called organic. In the interstellar medium, complex molecules are detected in the denser sources only. Although, with one exception, complex molecules have only been detected in the gas phase, there is strong evidence that they can be formed in ice mantles on interstellar grains. The nature of the gaseous complex species depends dramatically on the source where they are found: in cold, dense regions they tend to be unsaturated (hydrogen-poor) and exotic, whereas in young stellar objects, they tend to be quite saturated (hydrogen-rich) and terrestrial in nature. Based on both their spectra and chemistry, complex molecules are excellent probes of the physical conditions and history of the sources where they reside. Because they are detected in young stellar objects, complex molecules are expected to be common ingredients for new planetary systems. In this review, we discuss both the observation and chemistry of complex molecules in assorted interstellar regions in the Milky Way.

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Complex Organic Interstellar Molecules

Recent advances in the understanding of the chemical processes that occur during all stages of the formation of stars, from the collapse of molecular clouds to the assemblage of icy planetesimals in protoplanetary accretion disks, are reviewed. Observational studies of the circumstellar material within 100‐10,000 AU of the young star with (sub)millimeter single-dish telescopes, millimeter interferometers, and ground-based as well as space-borne infrared observatories have only become possible within the past few years. Results are compared with detailed chemical models that emphasize the coupling of gas-phase and grain-surface chemistry. Molecules that are particularly sensitive to different routes of formation and that may be useful in distinguishing between a variety of environments and histories are outlined. In the cold, low-density prestellar cores, radicals and long unsaturated carbon chains are enhanced. During the cold collapse phase, most species freeze out onto the grains in the high-density inner region. Once young stars ignite, their surroundings are heated through radiation and/or shocks, whereupon new chemical characteristics appear. Evaporation of ices drives a “hot core” chemistry rich in organic molecules, whereas shocks propagating through the dense envelope release both refractory and volatile grain material, resulting in prominent SiO, OH, and H2O emission. The role of future instrumentation in further developing these chemical and temporal diagnostics is discussed.

/pdf/chemical-evolution-of-star-forming-regions-2j830kxyvn.pdf

Chemical evolution of star-forming regions

Context. The discovery of amino acids in meteorites fallen to Earth and the detection of glycine, the simplest of them, in samples returned from a comet to Earth strongly suggest that the chemistry of the interstellar medium is capable of producing such complex organic molecules and that they may be widespread in our Galaxy. Aims. Our goal is to investigate the degree of chemical complexity that can be reached in the interstellar medium, in particular in dense star-forming regions. Methods. We performed an unbiased, spectral line survey toward Sgr B2(N) and (M), two regions where high-mass stars are formed, with the IRAM 30 m telescope in the 3 mm atmospheric transmission window. Partial surveys at 2 and 1.3 mm were performed in parallel. The spectra were analyzed with a simple radiative transfer model that assumes local thermodynamic equilibrium but takes optical depth effects into account. Results. About 3675 and 945 spectral lines with a peak signal-to-noise ratio higher than 4 are detected at 3 mm toward Sgr B2(N) and (M), i.e. about 102 and 26 lines per GHz, respectively. This represents an increase by about a factor of two over previous surveys of Sgr B2. About 70% and 47% of the lines detected toward Sgr B2(N) and (M) are identified and assigned to 56 and 46 distinct molecules as well as to 66 and 54 less abundant isotopologues of these molecules, respectively. In addition, we report the detection of transitions from 59 and 24 catalog entries corresponding to vibrationally or torsionally excited states of some of these molecules, respectively, up to a vibration energy of 1400 cm-1 (2000 K). Excitation temperatures and column densities were derived for each species but should be used with caution. The rotation temperatures of the detected complex molecules typically range from ~50 to 200 K. Among the detected molecules, aminoacetonitrile, n- propyl cyanide, and ethyl formate were reported for the first time in space based on this survey, as were five rare isotopologues of vinyl cyanide, cyanoacetylene, and hydrogen cyanide. We also report the detection of transitions from within twelve new vibrationally or torsionally excited states of known molecules. Absorption features produced by diffuse clouds along the line of sight are detected in transitions with low rotation quantum numbers of many simple molecules and are modeled with ~30–40 velocity components with typical linewidths of ~3–5 km s-1 . Conclusions. Although the large number of unidentified lines may still allow future identification of new molecules, we expect most of these lines to belong to vibrationally or torsionally excited states or to rare isotopologues of known molecules for which spectroscopic predictions are currently missing. Significant progress in extending the inventory of complex organic molecules in Sgr B2(N) and deriving tighter constraints on their location, origin, and abundance is expected in the near future thanks to an ongoing spectral line survey at 3 mm with ALMA in its cycles 0 and 1. The present single-dish survey will serve as a solid basis for the line identification and analysis of such an interferometric survey.

/pdf/complex-organic-molecules-in-the-interstellar-medium-iram-30-1xj4x1o7z6.pdf

Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M)

Context. Complex organic molecules (COMs) have long been detected in the interstellar medium, especially in hot cores and in the hot corinos of low-mass protostars. Their formation routes however remain uncertain. Both warm gas-phase reactions and warm grain-surface reactions have been invoked to account for their presence in low-mass protostars. In this latter scheme, COMs result from radical-radical reactions on the grains as radicals become mobile when the nascent protostar warms up its surroundings and the resulting molecules are subsequently desorbed into the gas phase at higher temperatures.Aims. Prestellar cores are the direct precursors of low-mass protostars and offer a unique opportunity to study the formation of COMs before the warm-up phase. Their very low temperatures (≤ 10 K) and the absence of any heating source or outflow exclude any efficient warm gas phase or warm dust chemistry, so that the presence of COMs in prestellar cores would have to originate from non-thermal chemical processes.Methods. We used the IRAM 30 m telescope to look for four O-bearing COMs (acetaldehyde CH3 CHO, dimethyl ether CH3 OCH3 , methyl formate CH3 OCHO, and ketene CH2 CO) in the prestellar core L1689B.Results. We report the unambiguous detection of all four molecules in the cold gas phase of L1689B. These detections support the role played by non-thermal (possibly photolytic) processes in COM formation and desorption, though the presence of dimethyl ether is so far unexplained by current grain formation scenarios. The data show univocally that COM synthesis has already started at the prestellar stage and suggests at least part of the COMs detected in hot corinos have a prestellar origin.

/pdf/detection-of-complex-organic-molecules-in-a-prestellar-core-llb9afw4j4.pdf

Detection of complex organic molecules in a prestellar core: a new challenge for astrochemical models

To date, 204 individual molecular species, comprised of 16 different elements, have been detected in the interstellar and circumstellar medium by astronomical observations. These molecules range in size from two atoms to seventy, and have been detected across the electromagnetic spectrum from cm-wavelengths to the ultraviolet. This census presents a summary of the first detection of each molecular species, including the observational facility, wavelength range, transitions, and enabling laboratory spectroscopic work, as well as listing tentative and disputed detections. Tables of molecules detected in interstellar ices, external galaxies, protoplanetary disks, and exoplanetary atmospheres are provided. A number of visual representations of this aggregate data are presented and briefly discussed in context.

2018 Census of Interstellar, Circumstellar, Extragalactic, Protoplanetary Disk, and Exoplanetary Molecules

More than 60 percent of the millimeter wave spectrum between 70 and 150 GHz of the giant Sgr B2 molecular cloud was surveyed with the Bell Laboratories 7 m telescope at a spectral resolution of 1 MHz. The observations and instrumentation are described, including beam efficiency and beamwidth as functions of frequency, frequency coverage, and rms noise. The catalog used to identify the 457 lines found is summarized, and the analysis of the data to determine column densities and rotational temperatures is discussed. The range of rotational temperatures obtained and their relation to the kinetic temperature, and their implications for the hydrogen density, are considered. More than 300 lines are transitions of 21 molecules, and the results for these are analyzed, giving excitation diagrams for most of them. A partly successful attempt is made to use ratios of the calculated abundances to predict abundances of as yet undetected species. Finally, the spectra for the entire survey are presented.

A Survey of the Millimeter-Wave Spectrum of Sagittarius B2

Observations of the K components of the CH3CN J = 4-to-3 rotational transition at 73.6 GHz, the 6-to-5 transition at 110.4 GHz, and the 7-to-6 transition at 128.7 GHz, yield a mean kinetic temperature value of 85 + or - 10 K and a mean H2 density of 110,000 + or - 50,000/cu cm for the central 2.0 arcmin of the Sgr B2 molecular cloud. Within the K = zero-to-4 ladders of CH3CN in Sgr B2, the populations of the radiatively coupled J levels are relaxed and exhibit a rotational temperature of about 16 K, which is similar to that of several linear molecules.

The kinetic temperature and density of the Sagittarius B2 molecular cloud from observations of methyl cyanide.

The identification of the 114,221-MHz line in the spectrum of the evolved carbon star IRC +10216 with a blend of the rotational transition of C4H and the first rotational transition of vibrationally excited CO is investigated. A spectrum of the source was obtained using an 11-m telescope in the range covering the N = 12 to 11 and 11 to 10 spin-doublet rotational transitions of C4H. Two peaks of equal intensity and width are found in each band, suggesting a spin rotation constant of 1.06 for the 12 to 11 doublet and 1.09 for the 11 to 10 doublet, and excluding the possibility that vibrationally excited CO made any contribution to the 12 to 11 doublet. An additional survey of the regions from 103.8 to 107.5 and 113.3 to 117.0 GHz has revealed no new lines stronger than 0.1 K in the spectrum of IRC +10216.

On C4H versus vibrationally excited CO in IRC + 10216

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A Survey of the Millimeter-Wave Spectrum of Sagittarius B2

The kinetic temperature and density of the Sagittarius B2 molecular cloud from observations of methyl cyanide.

On C4H versus vibrationally excited CO in IRC + 10216