Theoretical spectroscopic study of acetyl (CH3CO), vinoxy (CH2CHO), and 1-methylvinoxy (CH3COCH2) radicals. Barrierless formation processes of acetone in the gas phase

Background: Acetone is present in the earth´s atmosphere and extra-terrestrially. The knowledge of its chemical history in these environments represents a challenge with important implications for global tropospheric chemistry and astrochemistry. The results of a search for efficient barrierless pathways producing acetone from radicals in the gas phase are described in this paper. The spectroscopic properties of radicals needed for their experimental detection are provided. Methods: The reactants were acetone fragments of low stability and small species containing C, O and H atoms. Two exergonic bimolecular addition reactions involving the radicals CH3, CH3CO, and CH3COCH2, were found to be competitive according to the kinetic rates calculated at different temperatures. An extensive spectroscopic study of the radicals CH3COCH2 and CH3CO, as well as the CH2CHO isomer, was performed. Rovibrational parameters, anharmonic vibrational transitions, and excitations to the low-lying excited states are provided. For this purpose, RCCSD(T)-F12 and MRCI/CASSCF calculations were performed. In addition, since all the species presented non-rigid properties, a variational procedure of reduced dimensionality was employed to explore the far infrared region. Results: The internal rotation barriers were determined to be V3=143.7 cm-1 (CH3CO), V2=3838.7 cm-1 (CH2CHO) and V3=161.4 cm-1 and V2=2727.5 cm-1 (CH3COCH2).The splitting of the ground vibrational state due to the torsional barrier have been computed to be 2.997 cm-1, 0.0 cm-1, and 0.320 cm-1, for CH3CO, CH2CHO, and CH3COCH2, respectively. Conclusions: Two addition reactions, H+CH3COCH2 and CH3+CH3CO, could be considered barrierless formation processes of acetone after considering all the possible formation routes, starting from 58 selected reactants, which are fragments of the molecule. The spectroscopic study of the radicals involved in the formation processes present non-rigidity. The interconversion of their equilibrium geometries has important spectroscopic effects on CH3CO and CH3COCH2, but is negligible for CH2CHO.

Representing chemical history for ozone time-series predictions - a method development study for deep learning models

<p>Machine learning techniques like deep learning gained enormous momentum in recent years. This was mainly caused by the success story of the main drivers like image and speech recognition, video prediction and autonomous driving, to name just a few.<br>Air pollutant forecasting models are an example, where earth system scientists start picking up deep learning models to enhance the forecast quality of time series. Almost all previous air pollution forecasts with machine learning rely solely on analysing temporal features in the observed time series of the target compound(s) and additional variables describing precursor concentrations and meteorological conditions. These studies, therefore, neglect the "chemical history" of air masses, i.e. the fact that air pollutant concentrations at a given observation site are a result of emission and sink processes, mixing and chemical transformations along the transport pathways of air.<br>This study develops a concept of how such factors can be represented in the recently published deep learning model IntelliO3. The concept is demonstrated with numerical model data from the WRF-Chem model because the gridded model data provides an internally consistent dataset with complete spatial coverage and no missing values.<br>Furthermore, using model data allows for attributing changes of the forecasting performance to specific conceptual aspects. For example, we use the 8 wind sectors (N, NE, E, SE, etc.) and circles with predefined radii around our target locations to aggregate meteorological and chemical data from the intersections. Afterwards, we feed this aggregated data into a deep neural network while using the ozone concentration of the central point's next timesteps as targets. By analysing the change of forecast quality when moving from 4-dimensional (x, y, z, t) to 3-dimensional (x, y, t or r, φ, t) sectors and thinning out the underlying model data, we can deliver first estimates of expected performance gains or losses when applying our concept to station based surface observations in future studies.</p>

Isotopic fractionation study towards massive star-forming regions across the Galaxy

One of the most important tools to investigate the chemical history of our Galaxy and our own Solar System is to measure the isotopic fractionation of chemical elements. In the present study new astronomical observations devoted to the study of hydrogen and nitrogen fractionation (D/H and 14N/15N ratios) of molecules, towards massive star-forming regions in different evolutionary phases, have been presented. Moreover, a new detailed theoretical study of carbon fractionation, 12C/13C ratios, has been done. One of the main results was the confirmation that the 14N/15N ratio increases with the galactocentric distance, as predicted by stellar nucleosynthesis Galactic chemical evolution models. This work gives new important inputs on the understanding of local chemical processes that favor the production of molecules with different isotopes in star-forming regions.

Detailed abundances in a sample of very metal-poor stars

Context. Unevolved metal-poor stars bore witness to the early evolution of the Galaxy, and the determination of their detailed chemical composition is an important tool to understand its chemical history. The study of their chemical composition can also be used to constrain the nucleosynthesis of the first generation of supernovae that enriched the interstellar medium. Aims. We aim to observe a sample of extremely metal-poor star (EMP stars) candidates selected from the Sloan Digital Sky Survey data release 12 (SDSS DR12) and determine their chemical composition. Methods. We obtained high-resolution spectra of a sample of five stars using HDS on Subaru telescope and used standard 1D models to compute the abundances. The stars we analysed have a metallicity [Fe/H] of between −3.50 and −4.25 dex. Results. We confirm that the five metal-poor candidates selected from low-resolution spectra are very metal poor. We present the discovery of a new ultra metal-poor star (UMP star) with a metallicity of [Fe/H] = −4.25 dex (SDSS J1050032.34−241009.7). We measured in this star an upper limit of lithium (log(Li/H) ≤ 2.0. We found that the four most metal-poor stars of our sample have a lower lithium abundance than the Spite plateau lithium value. We obtain upper limits for carbon in the sample of stars. None of them belong to the high carbon band. We measured abundances of Mg and Ca in most of the stars and found three new α-poor stars.

The composition of hot Jupiter atmospheres assembled within chemically evolved protoplanetary discs

ABSTRACT The radial-dependent positions of snowlines of abundant oxygen- and carbon-bearing molecules in protoplanetary discs will result in systematic radial variations in the carbon-to-oxygen (C/O) ratios in the gas and ice. This variation is proposed as a tracer of the formation location of gas-giant planets. However, disc chemistry can affect the C/O ratios in the gas and ice, thus potentially erasing the chemical fingerprint of snowlines in gas-giant atmospheres. We calculate the molecular composition of hot Jupiter atmospheres using elemental abundances extracted from a chemical kinetics model of a disc mid-plane, where we have varied the initial abundances and ionization rates. The models predict a wider diversity of possible atmospheres than those predicted using elemental ratios from snowlines only. As found in previous work, as the C/O ratio exceeds the solar value, the mixing ratio of CH4 increases in the lower atmosphere, and those of C2H2 and HCN increase mainly in the upper atmosphere. The mixing ratio of H2O correspondingly decreases. We find that hot Jupiters with C/O > 1 can only form between the CO2 and CH4 snowlines. Moreover, they can only form in a disc which has fully inherited interstellar abundances, and where negligible chemistry has occurred. Hence, carbon-rich planets are likely rare, unless efficient transport of hydrocarbon-rich ices via pebble drift to within the CH4 snowline is a common phenomenon. We predict combinations of C/O ratios and elemental abundances that can constrain gas-giant planet formation locations relative to snowline positions, and that can provide insight into the disc chemical history.

ALMA observations of CS in NGC 1068: chemistry and excitation

ABSTRACT We present results from Atacama Large Millimeter/submillimeter Array (ALMA) observations of CS from the nearby galaxy NGC 1068 (∼14 Mpc). This Seyfert 2 barred galaxy possesses a circumnuclear disc (CND, r ∼ 200 pc) and a starburst ring (SB ring, r ∼ 1.3 kpc). These high-resolution maps (∼0.5 arcsec, ∼35 pc) allow us to analyse specific sub-regions in the galaxy and investigate differences in line intensity ratios and physical conditions, particularly those between the CND and SB ring. Local thermodynamic equilibrium (LTE) analysis of the gas is used to calculate CS densities in each sub-region, followed by the non-LTE analysis conducted using the radiative transfer code radex to fit observations and constrain gas temperature, CS column density and hydrogen density. Finally, the chemical code uclchem is used to reconstruct the gas, allowing an insight into its origin and chemical history. The density of hydrogen in the CND is found to be ≥105 cm−2, although exact values vary, reaching 106 cm−2 at the active galactic nucleus. The conditions in the two arms of the SB ring appear similar to one another, though the density found (∼104 cm−2) is lower than in the CND. The temperature in the CND increases from east to west, and is also overall greater than found in the SB ring. These modelling methods indicate the requirement for multiphase gas components in order to fit the observed emission over the galaxy. A larger number of high-resolution transitions across the SLED may allow for further constraining of the conditions, particularly in the SB ring.

Seeds of Life in Space (SOLIS)

Context. Low-mass protostars drive powerful molecular outflows that can be observed with millimetre and submillimetre telescopes. Various sulfuretted species are known to be bright in shocks and could be used to infer the physical and chemical conditions throughout the observed outflows. Aims. The evolution of sulfur chemistry is studied along the outflows driven by the NGC 1333-IRAS4A protobinary system located in the Perseus cloud to constrain the physical and chemical processes at work in shocks. Methods. We observed various transitions from OCS, CS, SO, and SO2 towards NGC 1333-IRAS4A in the 1.3, 2, and 3 mm bands using the IRAM NOrthern Extended Millimeter Array and we interpreted the observations through the use of the Paris-Durham shock model. Results. The targeted species clearly show different spatial emission along the two outflows driven by IRAS4A. OCS is brighter on small and large scales along the south outflow driven by IRAS4A1, whereas SO2 is detected rather along the outflow driven by IRAS4A2 that is extended along the north east–south west direction. SO is detected at extremely high radial velocity up to + 25 km s−1 relative to the source velocity, clearly allowing us to distinguish the two outflows on small scales. Column density ratio maps estimated from a rotational diagram analysis allowed us to confirm a clear gradient of the OCS/SO2 column density ratio between the IRAS4A1 and IRAS4A2 outflows. Analysis assuming non Local Thermodynamic Equilibrium of four SO2 transitions towards several SiO emission peaks suggests that the observed gas should be associated with densities higher than 105 cm−3 and relatively warm (T > 100 K) temperatures in most cases. Conclusions. The observed chemical differentiation between the two outflows of the IRAS4A system could be explained by a different chemical history. The outflow driven by IRAS4A1 is likely younger and more enriched in species initially formed in interstellar ices, such as OCS, and recently sputtered into the shock gas. In contrast, the longer and likely older outflow triggered by IRAS4A2 is more enriched in species that have a gas phase origin, such as SO2.