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.

/pdf/complex-organic-interstellar-molecules-sz3r2nq94z.pdf

Complex Organic Interstellar Molecules

We develop the use of the population diagram method to analyze molecular emission in order to derive physical properties of interstellar clouds. We focus particular attention on how the optical depth affects the derived total column density and the temperature. We derive an optical depth correction factor that can be evaluated based on observations and that incorporates the effect of saturation on derived upper level populations. We present analytic results for linear molecules in local thermodynamic equilibrium (LTE). We investigate numerically how subthermal excitation influences the population diagram technique, studying how the determination of kinetic temperature is affected when the local density is insufficient to achieve LTE. We present results for HC3N and CH3OH, representative of linear and nonlinear molecules, respectively. In some cases, alternative interpretations to the standard optically thin and thermalized picture yield significantly different results for column density and kinetic temperature, and we discuss this behavior. The population diagram method can be a very powerful tool for determining physical conditions in dense clouds if proper recognition is given to effects of saturation and subthermal excitation. We argue that the population diagram technique is, in fact, superior to fitting intensities of different transitions directly, and we indicate how it can be effectively employed.

https://iopscience.iop.org/article/10.1086/307195/pdf

Population Diagram Analysis of Molecular Line Emission

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)

Interstellar chemistry

Over 800 lines in OMC-1 and over 700 in Sgr B2 were observed in the NRAO 3-mm survey. Detailed LTE analysis of 33 species has been performed using numbers of transitions in the range 4-98. Limitations of the LTE optically thin approach are emphasized, in particular its failure to account for the anomalously strong emission from intrisically weak transitions in all the most complex species including CH3OHCO, (CH3)2O, CH3CHO, EtOH, NH2CHO, CH2CHCN, and EtCN. A detailed radiative-transfer analysis of all species with a sufficient number of transitions was also performed. The intensity and abundance ratios of the existing 3-mm surveys of Sgr B2 (NRAO, BTL) and OMC-1 (NRAO, Onsala) are compared to deduce the relative contributions to the emission of each molecular species from compact hot sources and from extended cool regions. It is concluded that the chemistries of the two regions are similar, which suggests a similar cosmic-ray flux, evolutionary stage, and elemental abundance distribution. 90 refs.

A Molecular Line Survey of Sagittarius B2 and Orion--KL from 70 to 115 GHz. II. Analysis of the Data

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A Molecular Line Survey of Sagittarius B2 and Orion--KL from 70 to 115 GHz. II. Analysis of the Data