Context. The inner regions of the envelopes surrounding young protostars are characterised 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, "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, 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 -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 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 13 C and deuterated isotopologues of glycolaldehyde are detected, also for the first time ever in the ISM. For the deuterated species a D/H ratio of ≈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 13 C-species lead to a 12 C: 13 C ratio of ≈30, lower than the typical ISM value. This low ratio may reflect an enhancement of 13 CO in the ice due to either ion-molecule reactions in the gas before freeze-out or differences in the temperatures where 12 CO and 13 CO ices sublimate. Conclusions. The results reinforce the importance of low temperature grain surfac...

UV-induced photodesorption of ice is a non-thermal evaporation process that can explain the presence of cold molecular gas in a range of interstellar regions. Information on the average UV photodesorption yield of astrophysically important ices exists for broadband UV lamp experiments. UV fields around low-mass pre-main sequence stars, around shocks and in many other astrophysical environments are however often dominated by discrete atomic and molecular emission lines. It is therefore crucial to consider the wavelength dependence of photodesorption yields and mechanisms. In this work, for the first time, the wavelength-dependent photodesorption of pure CO ice is explored between 90 and 170 nm. The experiments are performed under ultra high vacuum conditions using tunable synchrotron radiation. Ice photodesorption is simultaneously probed by infrared absorption spectroscopy in reflection mode of the ice and by quadrupole mass spectrometry of the gas phase. The experimental results for CO reveal a strong wavelength dependence directly linked to the vibronic transition strengths of CO ice, implying that photodesorption is induced by electronic transition (DIET). The observed dependence on the ice absorption spectra implies relatively low photodesorption yields at 121.6 nm (Lyman α), where CO barely absorbs, compared to the high yields found at wavelengths coinciding with transitions into the first electronic state of CO (A 1 Π at 150 nm); the CO photodesorption rates depend strongly on the UV profiles encountered in different star formation environments.

Formamide (NH 2 CHO) has previously been detected in several star-forming regions and is thought to be a precursor for different prebiotic molecules. Its formation mechanism is still debated, however. Observations of formamide, related species, and their isopotologues may provide useful clues to the chemical pathways leading to their formation. The Protostellar Interferometric Line Survey (PILS) represents an unbiased, high angular resolution and sensitivity spectral survey of the low-mass protostellar binary IRAS 16293-2422 with the Atacama Large Millimeter/submillimeter Array (ALMA). For the first time, we detect the three singly deuterated forms of NH 2 CHO (NH 2 CDO, cis-and trans-NHDCHO), as well as DNCO towards the component B of this binary source. The images reveal that the different isotopologues are all present in the same region. Based on observations of the 13 C isotopologues of formamide and a standard 12 C/ 13 C ratio, the deuterium fractionation is found to be similar for the three different forms with a value of about 2%. The DNCO/HNCO ratio is also comparable to the D/H ratio of formamide (∼1%). These results are in agreement with the hypothesis that NH 2 CHO and HNCO are chemically related through grain-surface formation.

Context. Ice desorption affects the evolution of the gas-phase chemistry during the protostellar stage, and also determines the chemical composition of comets forming in circumstellar disks. From observations, most volatile species are found in H 2 O-dominated ices. Aims. The aim of this study is first to experimentally determine how entrapment of volatiles in H 2 O ice depends on ice thickness, mixture ratio and heating rate, and second, to introduce an extended three-phase model (gas, ice surface and ice mantle) to describe ice mixture desorption with a minimum number of free parameters. Methods. Thermal H 2 O:CO 2 ice desorption is investigated in temperature programmed desorption experiments of thin (10-40 ML) ice mixtures under ultra-high vacuum conditions. Desorption is simultaneously monitored by mass spectrometry and reflection-absorption infrared spectroscopy. The H 2 O:CO 2 experiments are complemented with selected H 2 O:CO, and H 2 O:CO 2 :CO experiments. The results are modeled with rate equations that connect the gas, ice surface and ice mantle phases through surface desorption and mantlesurface diffusion.Results. The fraction of trapped CO 2 increases with ice thickness (10-32 ML) and H 2 O:CO 2 mixing ratio (5:1-10:1), but not with one order of magnitude different heating rates. The fraction of trapped CO 2 is 44-84% with respect to the initial CO 2 content for the investigated experimental conditions. This is reproduced quantitatively by the extended three-phase model that is introduced here. The H 2 O:CO and H 2 O:CO 2 :CO experiments are consistent with the H 2 O:CO 2 desorption trends, suggesting that the model can be used for other ice species found in the interstellar medium to significantly improve the parameterization of ice desorption.

Context.One of the open questions in astrochemistry is how complex organic and prebiotic molecules are formed. The unsurpassed sensitivity of the Atacama Large Millimeter/submillimeter Array (ALMA) takes the quest for discovering molecules in the warm and dense gas surrounding young stars to the next level. Aims. Our aim is to start the process of compiling an inventory of oxygen-bearing complex organic molecules toward the solar-type Class 0 protostellar binary IRAS 16293-2422 from an unbiased spectral survey with ALMA, Protostellar Interferometric Line Survey (PILS). Here we focus on the new detections of ethylene oxide (c-C 2 H 4 O), acetone (CH 3 COCH 3 ), and propanal (C 2 H 5 CHO). Methods. With ALMA, we surveyed the spectral range from 329 to 363 GHz at 0.5 (60 AU diameter) resolution. Using a simple model for the molecular emission in local thermodynamical equilibrium, the excitation temperatures and column densities of each species were constrained. Results. We successfully detect propanal (44 lines), ethylene oxide (20 lines) and acetone (186 lines) toward one component of the protostellar binary, IRAS16293B. The high resolution maps demonstrate that the emission for all investigated species originates from the compact central region close to the protostar. This, along with a derived common excitation temperature of T ex ≈ 125 K, is consistent with a coexistence of these molecules in the same gas. Conclusions. The observations mark the first detections of acetone, propanal and ethylene oxide toward a low-mass protostar. The relative abundance ratios of the two sets of isomers, a CH 3 COCH 3 /C 2 H 5 CHO ratio of 8 and a CH 3 CHO/c-C 2 H 4 O ratio of 12, are comparable to previous observations toward high-mass protostars. The majority of observed abundance ratios from these results as well as those measured toward high-mass protostars are up to an order of magnitude above the predictions from chemical models. This may reflect either missing reactions or uncertain rates in the chemical networks. The physical conditions, such as temperatures or densities, used in the models, may not be applicable to solar-type protostars either.

Context. Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims. N 2 and O 2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods. Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N 2 and O 2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N 2 and O 2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results. N 2 photodesorption mainly occurs through excitation of the b 1 Π u state and subsequent desorption of surface molecules. The observed vibronic structure in the N 2 photodesorption spectrum, together with the absence of N 3 formation, supports that the photodesorption mechanism of N 2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O 2 photodesorption in the 7−13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions. Photodesorption rates of N 2 and O 2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10 −3 and 10 −2 photodesorbed molecules per incoming photon.

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.

UV ice photodesorption is an important non-thermal desorption pathway in many interstellar environments that has been invoked to explain observations of cold molecules in disks, clouds and cloud cores. Systematic laboratory studies of the photodesorption rates, between 7 and 14 eV, from CO:N 2 binary ices, have been performed at the DESIRS vacuum UV beamline of the synchrotron facility SOLEIL. The photodesorption spectral analysis demonstrates that the photodesorption process is indirect, i.e. the desorption is induced by a photon absorption in sub-surface molecular layers, while only surface molecules are actually desorbing. The photodesorption spectra of CO and N 2 in binary ices therefore depend on the absorption spectra of the dominant species in the subsurface ice layer, which implies that the photodesorption efficiency and energy dependence are dramatically different for mixed and layered ices compared to pure ices. In particular, a thin (1-2 ML) N 2 ice layer on top of CO will effectively quench CO photodesorption, while enhancing N 2 photodesorption by a factors of a few (compared to the pure ices) when the ice is exposed to a typical dark cloud UV field, which may help to explain the different distributions of CO and N 2 H + in molecular cloud cores. This indirect photodesorption mechanism may also explain observations of small amounts of complex organics in cold interstellar environments.