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. The inner regions of the envelopes surrounding young protostars are characterized by a complex chemistry, with prebiotic molecules present on the scales where protoplanetary disks eventually may form. The Atacama Large Millimeter/submillimeter Array (ALMA) provides an unprecedented view of these regions zooming in on solar system scales of nearby protostars and mapping the emission from rare species. Aims. The goal is to introduce a systematic survey, the Protostellar Interferometric Line Survey (PILS), of the chemical complexity of one of the nearby astrochemical templates, the Class 0 protostellar binary IRAS 16293 2422, using ALMA in order to understand the origin of the complex molecules formed in its vicinity. In addition to presenting the overall survey, the analysis in this paper focuses on new results for the prebiotic molecule glycolaldehyde, its isomers, and rarer isotopologues and other related molecules. Methods. An unbiased spectral survey of IRAS 16293 2422 covering the full frequency range from 329 to 363 GHz (0.8 mm) has been obtained with ALMA, in addition to a few targeted observations at 3.0 and 1.3 mm. The data consist of full maps of the protostellar binary system with an angular resolution of 0.5 '' (60 AU diameter), a spectral resolution of 0.2 km s(-1), and a sensitivity of 4-5 mJy beam(-1) km s(-1), which is approximately two orders of magnitude better than any previous studies. Results. More than 10 000 features are detected toward one component in the protostellar binary, corresponding to an average line density of approximately one line per 3 km s(-1). Glycolaldehyde; its isomers, methyl formate and acetic acid; and its reduced alcohol, ethylene glycol, are clearly detected and their emission well-modeled with an excitation temperature of 300 K. For ethylene glycol both lowest state conformers, aGg' and gGg', are detected, the latter for the first time in the interstellar medium (ISM). The abundance of glycolaldehyde is comparable to or slightly larger than that of ethylene glycol. In comparison to the Galactic Center these two species are over-abundant relative to methanol, possibly an indication of formation of the species at low temperatures in CO-rich ices during the infall of the material toward the central protostar. Both C-13 and the deuterated isotopologues of glycolaldehyde are detected, also for the first time ever in the ISM. For the deuterated species, a D/H ratio of approximate to 5% is found with no differences between the deuteration in the different functional groups of glycolaldehyde, in contrast to previous estimates for methanol and recent suggestions of significant equilibration between water and-OH functional groups at high temperatures. Measurements of the C-13-species lead to a C-12:C-13 ratio of approximate to 30, lower than the typical ISM value. This low ratio may reflect an enhancement of (CO)-C-13 in the ice due to either ion-molecule reactions in the gas before freeze-out or to differences in the temperatures where (CO)-C-12 and (CO)-C-13 ices sublimate. Conclusions. The results reinforce the importance of low-temperature grain surface chemistry for the formation of prebiotic molecules seen here in the gas after sublimation of the entire ice mantle. Systematic surveys of the molecules thought to be chemically related, as well as the accurate measurements of their isotopic composition, hold strong promise for understanding the origin of prebiotic molecules in the earliest stages of young stars.

/pdf/the-alma-protostellar-interferometric-line-survey-pils-first-1w0b4u0joy.pdf

The ALMA Protostellar Interferometric Line Survey (PILS): First results from an unbiased submillimeter wavelength line survey of the Class 0 protostellar binary IRAS 16293-2422 with ALMA

Over the past five decades, radio astronomy has shown that molecular complexity is a natural outcome of interstellar chemistry, in particular in star forming regions. However, the pathways that lead to the formation of complex molecules are not completely understood and the depth of chemical complexity has not been entirely revealed. In addition, the sulfur chemistry in the dense interstellar medium is not well understood. 
We want to know the relative abundances of alkanethiols and alkanols in the Galactic Center source Sagittarius B2(N2), the northern hot molecular core in Sgr B2(N), whose relatively small line widths are favorable for studying the molecular complexity in space. 
We investigated spectroscopic parameter sets that were able to reproduce published laboratory rotational spectra of ethanethiol and studied effects that modify intensities in the predicted rotational spectrum of ethanol. We used the Atacama Large Millimeter Array (ALMA) in its Cycles~0 and 1 for a spectral line survey of Sagittarius B2(N) between 84 and 114.4 GHz. These data were analyzed by assuming local thermodynamic equilibrium (LTE) for each molecule. Our observations are supplemented by astrochemical modeling; a new network is used for the first time that includes reaction pathways for alkanethiols. 
The column density ratios involving methanol, ethanol, and methanethiol in Sgr B2(N2) are similar to values reported for Orion KL, but those involving ethanethiol are significantly different and suggest that the detection of ethanethiol reported toward Orion KL is uncertain. Our chemical model presently does not permit the prediction of sufficiently accurate column densities of alkanethiols or their ratios among alkanethiols and alkanols. Therefore, additional observational results are required to establish the level of C2H5SH in the dense and warm interstellar medium with certainty.

/pdf/exploring-molecular-complexity-with-alma-emoca-alkanethiols-137gdkr5ng.pdf

Exploring molecular complexity with ALMA (EMoCA): Alkanethiols and alkanols in Sagittarius B2(N2)

Context. Complex organic molecules are detected in many sources in the warm inner regions of envelopes surrounding deeply embedded protostars. Exactly how these species form remains an open question.Aims. This study aims to constrain the formation of complex organic molecules through comparisons of their abundances towards the Class 0 protostellar binary IRAS 16293–2422.Methods. We utilised observations from the ALMA Protostellar Interferometric Line Survey of IRAS 16293–2422. The species identification and the rotational temperature and column density estimation were derived by fitting the extracted spectra towards IRAS 16293–2422 A and IRAS 16293–2422 B with synthetic spectra. The majority of the work in this paper pertains to the analysis of IRAS 16293–2422 A for a comparison with the results from the other binary component, which have already been published.Results. We detect 15 different complex species, as well as 16 isotopologues towards the most luminous companion protostar IRAS 16293–2422 A. Tentative detections of an additional 11 isotopologues are reported. We also searched for and report on the first detections of methoxymethanol (CH3 OCH2 OH) and trans-ethyl methyl ether (t-C2 H5 OCH3 ) towards IRAS 16293–2422 B and the follow-up detection of deuterated isotopologues of acetaldehyde (CH2 DCHO and CH3 CDO). Twenty-four lines of doubly-deuterated methanol (CHD2 OH) are also identified.Conclusions. The comparison between the two protostars of the binary system shows significant differences in abundance for some of the species, which are partially correlated to their spatial distribution. The spatial distribution is consistent with the sublimation temperature of the species; those with higher expected sublimation temperatures are located in the most compact region of the hot corino towards IRAS 16293–2422 A. This spatial differentiation is not resolved in IRAS 16293–2422 B and will require observations at a higher angular resolution. In parallel, the list of identified CHD2 OH lines shows the need of accurate spectroscopic data including their line strength.

/pdf/the-alma-pils-survey-inventory-of-complex-organic-molecules-2yabnoign2.pdf

The ALMA-PILS survey: inventory of complex organic molecules towards IRAS 16293–2422 A

This paper presents a systematic survey of the deuterated and 13C isotopologues of a variety of oxygen-bearing complex organic molecules on Solar System scales toward the protostar IRAS 16293-2422B. We use the data from an unbiased molecular line survey between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The observations probe scales of 60 AU where most of the organic molecules have sublimated off dust grains and are present in the gas-phase. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of approximately 2% and the other, the more complex species, D/H ratios of 4-8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short time-scale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 K and 300 K. This likely reflects the binding energies/sublimation temperatures of the individual species, in good agreement to what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species.

/pdf/the-alma-pils-survey-isotopic-composition-of-oxygen-2bn4qaz44b.pdf

The ALMA-PILS survey: Isotopic composition of oxygen-containing complex organic molecules toward IRAS 16293-2422B.

Glycolaldehyde, a sugar-related interstellar prebiotic molecule, has recently been detected in two star-forming regions, Sgr B2(N) and G31.41+0.31. The detection of this new species increased the list of complex organic molecules detected in the interstellar medium (ISM) and adds another level to the chemical complexity present in space. Besides, this kind of organic molecule is important because it is directly linked to the origin of life. For many years, astronomers have been struggling to understand the origin of this high chemical complexity in the ISM. The study of deuteration may provide crucial hints. In this context, we have measured the spectra of deuterated isotopologues of glycolaldehyde in the laboratory: the three monodeuterated ones (CH2OD-CHO, CHDOH-CHO and CH2OH-CDO) and one dideuterated derivative (CHDOH-CDO) in the ground vibrational state. Previous laboratory work on the D-isotopologues of glycolaldehyde was restricted to less than 26 GHz. We used a solidstate submillimeter-wave spectrometer in Lille with an accuracy for isolated lines better than 30 kHz to acquire new spectroscopic data between 150 and 630 GHz and employed the ASFIT and SPCAT programs for analysis. We measured around 900 new lines for each isotopologue and determined spectroscopic parameters. This allows an accurate prediction in the ALMA range up to 850 GHz. This treatment meets the needs for a first astrophysical research, for which we provide an appropriate set of predictions.

/pdf/the-submillimeter-spectrum-of-deuterated-glycolaldehydes-381y2bh87r.pdf

The submillimeter spectrum of deuterated glycolaldehydes

Context. Glycolaldehyde, a sugar-related interstellar prebiotic molecule, has recently been detected in two star-forming regions, Sgr B2(N) and G31.41+0.31. The detection of this new species increased the list of complex organic molecules detected in the interstellar medium (ISM) and adds another level to the chemical complexity present in space. Besides, this kind of organic molecule is important because it is directly linked to the origin of life. For many years, astronomers have been struggling to understand the origin of this high chemical complexity in the ISM. The study of deuteration may provide crucial hints. Aims: In this context, we have measured the spectra of deuterated isotopologues of glycolaldehyde in the laboratory: the three mono-deuterated ones (CH2OD-CHO, CHDOH-CHO and CH2OH-CDO) and one dideuterated derivative (CHDOH-CDO) in the ground vibrational state. Methods: Previous laboratory work on the D-isotopologues of glycolaldehyde was restricted to less than 26 GHz. We used a solid-state submillimeter-wave spectrometer in Lille with an accuracy for isolated lines better than 30 kHz to acquire new spectroscopic data between 150 and 630 GHz and employed the ASFIT and SPCAT programs for analysis. Results: We measured around 900 new lines for each isotopologue and determined spectroscopic parameters. This allows an accurate prediction in the ALMA range up to 850 GHz. Conclusions: This treatment meets the needs for a first astrophysical research, for which we provide an appropriate set of predictions. Full Table 2 and Tables 3-5 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/540/A51

/pdf/the-submillimeter-spectrum-of-deuterated-glycolaldehydes-1uqhua168a.pdf

The rotational spectra of the two monosubstituted 13C isotopologues of the anti conformer of ethanol have been measured between 80–800 GHz using three different spectrometers at the Cologne Laboratory Astrophysics group. The dataset was constrained for fitting with a standard Watson-S reduction Hamiltonian by rejecting transitions from high-lying states showing significant perturbation with the gauche states and by averaging some small methyl torsional splits. This treatment is compatible with the needs for a first astrophysical research for which an appropriate set of predictions is given.

Millimetre-wave spectrum of anti-13C1 and 13C2 isotopologues of ethanol

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The submillimeter spectrum of deuterated glycolaldehydes

The submillimeter spectrum of deuterated glycolaldehydes

Millimetre-wave spectrum of anti-13C1 and 13C2 isotopologues of ethanol