Complex organic molecules (COMs) have been detected in a variety of environments including cold prestellar cores. Given the low temperatures of these objects, these detections challenge existing ...models. We report here new observations toward the prestellar core L1544. They are based on an unbiased spectral survey of the 3 mm band at the IRAM 30 m telescope as part of the Large Program ASAI. The observations allow us to provide a full census of the oxygen-bearing COMs in this source. We detected tricarbon monoxide, methanol, acetaldehyde, formic acid, ketene, and propyne with abundances varying from 5 x 10 super(-11) to 6 x 10 super(-9). The non-LTE analysis of the methanol lines shows that they are likely emitted at the border of the core at a radius of ~8000 AU, where T ~ 10 K and n sub(H2) ~ 2 x 10 super(4) cm super(-3). Previous works have shown that water vapor is enhanced in the same region because of the photodesorption of water ices. We propose that a non-thermal desorption mechanism is also responsible for the observed emission of methanol and COMs from the same layer. The desorbed oxygen and a small amount of desorbed methanol and ethene are enough to reproduce the abundances of tricarbon monoxide, methanol, acetaldehyde, and ketene measured in L1544. These new findings open the possibility that COMs in prestellar cores originate in a similar outer layer rather than in the dense inner cores, as previously assumed, and that their formation is driven by the non-thermally desorbed species.
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 CH3CHO, dimethyl ether CH3OCH3, methyl formate CH3OCHO, and ketene CH2CO) 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.
Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules ...which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (gap30-40 K) and released in the gas phase at dust temperatures of gap100 K. However, recent detections of COMs in lap20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we present a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS 16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (lap30 K) envelope of IRAS 16293-2422, with abundances of 0.03-2 x 10 super(-10). Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.
Abstract
We report on a systematic search for oxygen-bearing complex organic molecules (COMs) in the solar-like protostellar shock region L1157-B1, as part of the IRAM Large Program ‘Astrochemical ...Surveys At IRAM’. Several COMs are unambiguously detected, some for the first time, such as ketene H2CCO, dimethyl ether (CH3OCH3) and glycolaldehyde (HCOCH2OH), and others firmly confirmed, such as formic acid (HCOOH) and ethanol (C2H5OH). Thanks to the high sensitivity of the observations and full coverage of the 1, 2 and 3 mm wavelength bands, we detected numerous (∼10–125) lines from each of the detected species. Based on a simple rotational diagram analysis, we derive the excitation conditions and the column densities of the detected COMs. Combining our new results with those previously obtained towards other protostellar objects, we found a good correlation between ethanol, methanol and glycolaldehyde. We discuss the implications of these results on the possible formation routes of ethanol and glycolaldehyde.
Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a ...series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.
New insights into the formation of interstellar formamide, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction NH2 + ...H2CO → NH2CHO + H. Contrarily to what previously suggested, this reaction is essentially barrierless and can, therefore, occur under the low temperature conditions of intestellar objects thus providing a facile formation route of formamide. The rate coefficient parameters for the reaction channel leading to NH2CHO + H have been calculated to be A = 2.6 × 10−12 cm3 s−1, β = −2.1 and γ = 26.9 K in the range of temperatures 10–300 K. Including these new kinetic data in a refined astrochemical model, we show that the proposed mechanism can well reproduce the abundances of formamide observed in two very different interstellar objects: the cold envelope of the Sun-like protostar IRAS16293−2422 and the molecular shock L1157-B2. Therefore, the major conclusion of this Letter is that there is no need to invoke grain-surface chemistry to explain the presence of formamide provided that its precursors, NH2 and H2CO, are available in the gas phase.
Formamide (NH sub(2)CHO), the simplest possible amide, has recently been suggested to be a central species in the synthesis of metabolic and genetic molecules, the chemical basis of life. In this ...Letter, we report the first detection of formamide in a protostar, IRAS 16293-2422, which may be similar to the Sun and solar system progenitor. The data combine spectra from the millimeter and submillimeter TIMASSS survey with recent, more sensitive observations at the IRAM 30 m telescope. With an abundance relative to H sub(2) of ~10 super(-10), formamide appears as abundant in this solar-type protostar as in the two high-mass star-forming regions, Orion-KL and SgrB2, where this species has previously been detected. Given the largely different UV-illuminated environments of the three sources, the relevance of UV photolysis of interstellar ices in the synthesis of formamide is therefore questionable. Assuming that this species is formed in the gas phase via the neutral-neutral reaction between the radical NH sub(2) and H sub(2)CO, we predict an abundance in good agreement with the value derived from our observations. The comparison of the relative abundance NH sub(2)CHO/H sub(2)O in IRAS 16293-2422 and in the coma of the comet Hale-Bopp supports the similarity between interstellar and cometary chemistry. Our results thus suggest that the abundance of some cometary organic volatiles could reflect gas phase rather than grain-surface interstellar chemistry.
Abstract
Based on recent work, formamide might be a potentially very important molecule in the emergence of terrestrial life. Although detected in the interstellar medium for decades, its formation ...route is still debated, whether in the gas phase or on the dust grain surfaces. Molecular deuteration has proven to be, in other cases, an efficient way to identify how a molecule is synthesized. For formamide, new published observations towards the IRAS16293-2422 B hot corino show that its three deuterated forms have all the same deuteration ratio, 2–5 per cent and that this is a factor of 3–8 smaller than that measured for H2CO towards the IRAS16293-2422 protostar. Following a previous work on the gas-phase formamide formation via the reaction NH2 + H2CO → HCONH2 + H, we present here new calculations of the rate coefficients for the production of monodeuterated formamide through the same reaction, starting from monodeuterated NH2 or H2CO. Some misconceptions regarding our previous treatment of the reaction are also cleared up. The results of the new computations show that, at the 100 K temperature of the hot corino, the rate of deuteration of the three forms is the same, within 20 per cent. On the contrary, the reaction between non-deuterated species proceeds three times faster than that with deuterated ones. These results confirm that a gas-phase route for the formation of formamide is perfectly in agreement with the available observations.
The ratio between the two stable isotopes of nitrogen, 14N and 15N, is well measured in the terrestrial atmosphere (~272), and for the pre-solar nebula (~441, deduced from the solar wind). ...Interestingly, some pristine solar system materials show enrichments in 15N with respect to the pre-solar nebula value. However, it is not yet clear if and how these enrichments are linked to the past chemical history because we have only a limited number of measurements in dense star-forming regions. In this respect, dense cores, which are believed to be the precursors of clusters and also contain intermediate- and high-mass stars, are important targets because the solar system was probably born within a rich stellar cluster, and such clusters are formed in high-mass star-forming regions. The number of observations in such high-mass dense cores has remained limited so far. In this work, we show the results of IRAM-30 m observations of the J = 1−0 rotational transition of the molecules HCN and HNC and their 15N-bearing counterparts towards 27 intermediate- and high-mass dense cores that are divided almost equally into three evolutionary categories: high-mass starless cores, high-mass protostellar objects, and ultra-compact Hii regions. We have also observed the DNC(2–1) rotational transition in order to search for a relation between the isotopic ratios D/H and 14N/15N. We derive average 14N/15N ratios of 359 ± 16 in HCN and of 438 ± 21 in HNC, with a dispersion of about 150–200. We find no trend of the 14N/15N ratio with evolutionary stage. This result agrees with what has been found for N2H+ and its isotopologues in the same sources, although the 14N/15N ratios from N2H+ show a higher dispersion than in HCN/HNC, and on average, their uncertainties are larger as well. Moreover, we have found no correlation between D/H and 14N/15N in HNC. These findings indicate that (1) the chemical evolution does not seem to play a role in the fractionation of nitrogen, and that (2) the fractionation of hydrogen and nitrogen in these objects is not related.
We present the first census of the interstellar Complex Organic Molecules (iCOMs) in the low-mass Class I protostar SVS13-A, obtained by analysing data from the IRAM-30 m Large Project ASAI ...(Astrochemical Surveys At IRAM). They consist of a high-sensitivity unbiased spectral survey at the 1mm, 2mm, and 3mm IRAM bands. We detected five iCOMs: acetaldehyde (CH3CHO), methyl formate (HCOOCH3), dimethyl ether (CH3OCH3), ethanol (CH3CH2OH), and formamide (NH2CHO). In addition, we searched for other iCOMs and ketene (H2CCO), formic acid (HCOOH) and methoxy (CH3O), whose only ketene was detected. The numerous detected lines, from 5 to 37 depending on the species, cover a large upper level energy range, between 15 and 254 K. This allowed us to carry out a rotational diagram analysis and derive rotational temperatures between 35 and 110 K, and column densities between 3 × 1015 and 1 × 1017 cm−2 on the 0.3 arcsec size previously determined by interferometric observations of glycolaldehyde. These new observations clearly demonstrate the presence of a rich chemistry in the hot corino towards SVS13-A. The measured iCOMs abundances were compared to other Class 0 and I hot corinos, as well as comets, previously published in the literature. We find evidence that (i) SVS13-A is as chemically rich as younger Class 0 protostars, and (ii) the iCOMs relative abundances do not substantially evolve during the protostellar phase.