We present the fifth release of the UMIST Database for Astrochemistry (UDfA). The new reaction network contains 6173 gas-phase reactions, involving 467 species, 47 of which are new to this release. We have updated rate coefficients across all reaction types. We have included 1171 new anion reactions and updated and reviewed all photorates. In addition to the usual reaction network, we also now include, for download, state-specific deuterated rate coefficients, deuterium exchange reactions and a list of surface binding energies for many neutral species. Where possible, we have referenced the original source of all new and existing data. We have tested the main reaction network using a dark cloud model and a carbon-rich circumstellar envelope model. We present and briefly discuss the results of these models.

The UMIST database for astrochemistry 2012

Context. Little is known about the chemistry of isocyanates (compounds with the functional group R-N=C=O) in the interstellar medium (ISM), as only four of them have been detected so far: isocyanate radical (NCO), isocyanic acid (HNCO), N-protonated isocyanic acid (H2 NCO+ ), and methyl isocyanate (CH3 NCO). The molecular cloud G+0.693-0.027, located in the Galactic Centre, represents an excellent candidate to search for new isocyanates since it exhibits high abundances of the simplest ones, HNCO and CH3 NCO.Aims. After CH3 NCO, the next most complex isocyanates are ethyl isocyanate (C2 H5 NCO) and vinyl isocyanate (C2 H3 NCO). Their detection in the ISM would enhance our understanding of the formation of these compounds in space.Methods. We have searched for C2 H5 NCO, H2 NCO+ , C2 H3 NCO, and cyanogen isocyanate (NCNCO) in a sensitive unbiased spectral survey carried out in the 2 mm and 7 mm radio windows using the IRAM 30m and Yebes 40m radio telescopes, respectively.Results. We have detected C2 H5 NCO and H2 NCO+ towards G+0.693-0.027 (the former for the first time in the ISM) with molecular abundances of (4.7–7.3) × 10−11 and (1.0–1.5) × 10−11 , respectively. A ratio of CH3 NCO/C2 H5 NCO = 8 ± 1 is obtained; therefore, the relative abundance determined for HNCO:CH3 NCO:C2 H5 NCO is 1:1/55:1/447, which implies a decrease by more than one order of magnitude, going progressively from HNCO to CH3 NCO and to C2 H5 NCO. This is similar to what has been found for alcohols and thiols, for example, and suggests that C2 H5 NCO is likely formed on the surface of dust grains. In addition, we have obtained column density ratios of HNCO/NCO > 269, HNCO/H2 NCO+ ∼ 2100, and C2 H3 NCO/C2 H5 NCO < 4. A comparison of the methyl/ethyl ratios for isocyanates (-NCO), alcohols (-OH), formiates (HCOO-), nitriles (-CN), and thiols (-SH) is performed and shows that ethyl derivatives may be formed more efficiently for the N-bearing molecules than for the O- and S-bearing molecules.

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First detection of C2H5NCO in the ISM and search of other isocyanates towards the G+0.693-0.027 molecular cloud

Context. Peptide-like bond molecules, which can take part in the formation of proteins in a primitive Earth environment, have been detected only towards a few hot cores and hot corinos up to now.Aims. We present a study of HNCO, HC(O)NH2 , CH3 NCO, CH3 C(O)NH2 , CH3 NHCHO, CH3 CH2 NCO, NH2 C(O)NH2 , NH2 C(O)CN, and HOCH2 C(O)NH2 towards the hot core G31.41+0.31. The aim of this work is to study these species together to allow a consistent study among them.Methods. We have used the spectrum obtained from the ALMA 3 mm spectral survey GUAPOS, with a spectral resolution of ~0.488 MHz (~1.3–1.7 km s−1 ) and an angular resolution of 1.′′2 × 1.′′2 (~4500 au), to derive column densities of all the molecular species presented in this work, together with 0.′′2 × 0.′′2 (~750 au) ALMA observations from another project to study the morphology of HNCO, HC(O)NH2 , and CH3 C(O)NH2 .Results. We have detected HNCO, HC(O)NH2 , CH3 NCO, CH3 C(O)NH2 , and CH3 NHCHO, but no CH3 CH2 NCO, NH2 C(O)NH2 , NH2 C(O)CN, or HOCH2 C(O)NH2 . This is the first time that these molecules have been detected all together outside the Galactic centre. We have obtained molecular fractional abundances with respect to H2 from 10−7 down to a few 10−9 and abundances with respect to CH3 OH from 10−3 to ~4 × 10−2 , and their emission is found to be compact (~2′′, i.e. ~7500 au). From the comparison with other sources, we find that regions in an earlier stage of evolution, such as pre-stellar cores, show abundances at least two orders of magnitude lower than those in hot cores, hot corinos, or shocked regions. Moreover, molecular abundance ratios towards different sources are found to be consistent between them within ~1 order of magnitude, regardless of the physical properties (e.g. different masses and luminosities), or the source position throughout the Galaxy. Correlations have also been found between HNCO and HC(O)NH2 as well as CH3 NCO and HNCO abundances, and for the first time between CH3 NCO and HC(O)NH2 , CH3 C(O)NH2 and HNCO, and CH3 C(O)NH2 and HC(O)NH2 abundances. These results suggest that all these species are formed on grain surfaces in early evolutionary stages of molecular clouds, and that they are subsequently released back to the gas phase through thermal desorption or shock-triggered desorption.

The GUAPOS project - II. A comprehensive study of peptide-like bond molecules

Little is known about the chemistry of isocyanates (compounds with the functional group R-N=C=O) in the interstellar medium, as only four of them have been detected so far: isocyanate radical (NCO), isocyanic acid (HNCO), N-protonated isocyanic acid (H$_2$NCO$^+$) and methyl isocyanate (CH$_3$NCO). The molecular cloud G+0.693-0.027, located in the Galactic Centre, represents an excellent candidate to search for new isocyanates since it exhibits high abundances of the simplest ones, HNCO and CH$_3$NCO. After CH$_3$NCO, the next complex isocyanates are ethyl isocyanate (C$_2$H$_5$NCO) and vinyl isocyanate (C$_2$H$_3$NCO). Their detection in the ISM would enhance our understanding of the formation of these compounds in space. We have detected C$_2$H$_5$NCO and H$_2$NCO$^+$ towards G+0.693-0.027 (the former for the first time in the interstellar medium) with molecular abundances of (4.7$-$7.3)$\times$10$^{-11}$ and (1.0$-$1.5)$\times$10$^{-11}$, respectively. A ratio CH$_3$NCO / C$_2$H$_5$NCO = 8$\pm$1 is obtained; therefore the relative abundance determined for HNCO:CH$_3$NCO:C$_2$H$_5$NCO is 1:1/55:1/447, which implies a decrease by more than one order of magnitude going progressively from HNCO to CH$_3$NCO and to C$_2$H$_5$NCO. This is similar to what has been found for e.g. alcohols and thiols and suggests that C$_2$H$_5$NCO is likely formed on the surface of dust grains. In addition, we have obtained column density ratios of HNCO / NCO > 269, HNCO / H$_2$NCO$^+$ $\sim$ 2100 and C$_2$H$_3$NCO / C$_2$H$_5$NCO~<~4. A comparison of the Methyl~/~Ethyl ratios for isocyanates (-NCO), alcohols (-OH), formiates (HCOO-), nitriles (-CN) and thiols (-SH) is performed and shows that ethyl-derivatives may be formed more efficiently for the N-bearing molecules than for the O- and S-bearing molecules.

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First detection of C$_2$H$_5$NCO in the ISM and search of other isocyanates towards the G+0.693-0.027 molecular cloud.

Aims. Methyl isocyanate (CH3 NCO) and glycolonitrile (HOCH2 CN) are isomers and prebiotic molecules that are involved in the formation of peptide structures and the nucleobase adenine, respectively. These two species are investigated to study the interstellar chemistry of cyanides (CN) and isocyanates (NCO) and to gain insight into the reservoir of interstellar prebiotic molecules.Methods. ALMA observations of the intermediate-mass Class 0 protostar Serpens SMM1-a and ALMA-PILS data of the low-mass Class 0 protostar IRAS 16293B are used. Spectra are analysed with the CASSIS line analysis software package in order to identify and characterise molecules.Results. CH3 NCO, HOCH2 CN, and various other molecules are detected towards SMM1-a. HOCH2 CN is identified in the PILS data towards IRAS 16293B in a spectrum extracted at a half-beam offset position from the peak continuum. CH3 NCO and HOCH2 CN are equally abundant in SMM1-a at [X]/[CH3 OH] of 5.3 × 10−4 and 6.2 × 10−4 , respectively. A comparison between SMM1-a and IRAS 16293B shows that HOCH2 CN and HNCO are more abundant in the former source, but CH3 NCO abundances do not differ significantly. Data from other sources are used to show that the [CH3 NCO]/[HNCO] ratio is similar in all these sources within ~10%.Conclusions. The new detections of CH3 NCO and HOCH2 CN are additional evidence for a large interstellar reservoir of prebiotic molecules that can contribute to the formation of biomolecules on planets. The equal abundances of these molecules in SMM1-a indicate that their formation is driven by kinetic processes instead of thermodynamic equilibrium, which would drive the chemistry to one product. HOCH2 CN is found to be much more abundant in SMM1-a than in IRAS 16293B. From the observational data, it is difficult to indicate a formation pathway for HOCH2 CN, but the thermal Strecker-like reaction of CN− with H2 CO is a possibility. The similar [CH3 NCO]/[HNCO] ratios found in the available sample of studied interstellar sources indicate that these two species are either chemically related or their formation is affected by physical conditions in the same way. Both species likely form early during star formation, presumably via ice mantle reactions taking place in the dark cloud or when ice mantles are being heated in the hot core. The relatively high abundances of HOCH2 CN and HNCO in SMM1-a may be explained by a prolonged stage of relatively warm ice mantles, where thermal and energetic processing of HCN in the ice results in the efficient formation of both species.

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The prebiotic molecular inventory of Serpens SMM1 - I. An investigation of the isomers CH3NCO and HOCH2CN

After hydrogen, oxygen, and carbon, nitrogen is one of the most chemically active species in the interstellar medium (ISM). Nitrogen bearing molecules have great importance as they are actively involved in the formation of biomolecules. Therefore, it is essential to look for nitrogen-bearing species in various astrophysical sources, specifically around high-mass star-forming regions where the evolutionary history is comparatively poorly understood. In this paper, we report the observation of three potential pre-biotic molecules, namely, isocyanic acid (HNCO), formamide (NH2CHO), and methyl isocyanate (CH3NCO), which contain peptide-like bonds (-NH-C(=O)-) in a hot molecular core, G10.47+0.03 (hereafter, G10). Along with the identification of these three complex nitrogen-bearing species, we speculate their spatial distribution in the source and discuss their possible formation pathways under such conditions. The rotational diagram method under the LTE condition has been employed to estimate the excitation temperature and the column density of the observed species. Markov Chain Monte Carlo method was used to obtain the best suited physical parameters of G10 as well as line properties of some species. We also determined the hydrogen column density and the optical depth for different continuum observed in various frequency ranges. Finally, based on these observational results, we have constructed a chemical model to explain the observational findings. We found that HNCO, NH2CHO, and CH3NCO are chemically linked with each other.

Identification of pre-biotic molecules containing Peptide-like bond in a hot molecular core, G10.47+0.03

Identification of Prebiotic Molecules Containing Peptide-like Bonds in a Hot Molecular Core, G10.47+0.03

The abundance of interstellar ice constituents is usually expressed with respect to the water ice because, in denser regions, a significant portion of the interstellar grain surface would be covered by water ice. The binding energy (BE) or adsorption energy of the interstellar species regulates the chemical complexity of the interstellar grain mantle. Due to the high abundance of water ice, the BE of surface species with the water is usually provided and widely used in astrochemical modeling. However, the hydrogen molecules would cover some part of the grain mantle in the denser and colder part of the interstellar medium. Even at around similar to 10 K, few atoms and simple molecules with lower adsorption energies can migrate through the surface. The BE of the surface species with H-2 substrate would be very different from that of a water substrate. However, adequate information regarding these differences is lacking. Here, we employ the quantum chemical calculation to provide the BE of 95 interstellar species with H-2 substrate. These are representative of the BEs of species to a H-2 overlayer on a grain surface. On average, we notice that the BE with the H-2 monomer substrate is almost ten times lower than the BE of these species reported earlier with the H2O c-tetramer configuration. The encounter desorption of H and H-2 was introduced [with E-D (H, H-2) = 45 K and E-D (H-2, H-2) = 23 K] to have a realistic estimation of the abundances of the surface species in the colder and denser region. Our quantum chemical calculations yield higher adsorption energy of H-2 than that of H [E-D (H, H-2) = 23-25 K and E-D (H-2, H-2) = 67-79 K]. We further implement an astrochemical model to study the effect of encounter desorption with the present realistic estimation. The encounter desorption of the N atom [calculations yield E-D (N, H-2) = 83 K] is introduced to study the differences with its inclusion.

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Effect of Binding Energies on the Encounter Desorption

Phosphorus related species are not known to be as omnipresent in space as hydrogen, carbon, nitrogen, oxygen, and sulfur-bearing species. Astronomers spotted very few P-bearing molecules in the interstellar medium and circumstellar envelopes. Limited discovery of the P-bearing species imposes severe constraints in modeling the P-chemistry. In this paper, we carry out extensive chemical models to follow the fate of P-bearing species in diffuse clouds, photon-dominated or photodissociation regions (PDRs), and hot cores/corinos. We notice a curious correlation between the abundances of PO and PN and atomic nitrogen. Since N atoms are comparatively abundant in diffuse clouds and PDRs than in the hot core/corino region, PO/PN reflects 1 in the late warm-up evolutionary phase of the hot core/corino regions. During the end of the post-warm-up phase, we obtain PO/PN > 1 for hot core and < 1 for its low mass analog. We employ a radiative transfer model to investigate the transitions of some of the P-bearing species in diffuse cloud and hot core regions and estimate the line profiles. Our study estimates the required integration time to observe these transitions with ground-based and space-based telescopes. We also carry out quantum chemical computation of the infrared features of PH3 along with various impurities. We notice that SO2 overlaps with the PH3 bending-scissoring modes around ~ (1000 - 1100) cm-1. We also find that the presence of CO2 can strongly influence the intensity of the stretching modes around ~ 2400 cm-1 of PH3 .

Chemical Complexity of Phosphorous-bearing Species in Various Regions of the Interstellar Medium

It is speculated that there might be some linkage between interstellar aldehydes and their corresponding alcohols. Here, an observational study and astrochemical modeling are coupled together to illustrate the connection between them. The ALMA Cycle 4 data of a hot molecular core, G10.47+0.03 is utilized for this study. Various aldehydes (acetaldehyde, propanal, and glycolaldehyde), alcohols (methanol and ethylene glycol), and a ketone (acetone) are identified in this source. The excitation temperatures and the column densities of these species were derived via the rotation diagram method assuming LTE conditions. An extensive investigation is carried out to understand the formation of these species. Six pairs of aldehyde-alcohol: i) methanal and methanol; ii) ethanal and ethanol; iii) propanal and 1-propanol; iv) propenal and allyl alcohol; v) propynal and propargyl alcohol; vi) glycolaldehyde and ethylene glycol; vii) along with one pair of ketone-alcohol (acetone and isopropanol) and viii) ketene-alcohol (ethenone and vinyl alcohol) are considered for this study. Two successive hydrogenation reactions in the ice phase are examined to form these alcohols from aldehydes, ketone, and ketene, respectively. Quantum chemical methods are extensively executed to review the ice phase formation route and the kinetics of these species. Based on the obtained kinetic data, astrochemical modeling is employed to derive the abundances of these aldehydes, alcohols, ketone, and ketene in this source. It is seen that our model could successfully explain the observed abundances of various species in this hot molecular core.

Rana Ghosh

Papers

Identification of pre-biotic molecules containing Peptide-like bond in a hot molecular core, G10.47+0.03

Identification of Prebiotic Molecules Containing Peptide-like Bonds in a Hot Molecular Core, G10.47+0.03

Effect of Binding Energies on the Encounter Desorption

Chemical Complexity of Phosphorous-bearing Species in Various Regions of the Interstellar Medium

Is There Any Linkage between Interstellar Aldehyde and Alcohol