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We provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high-accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring-opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered. These findings are discussed in light of the early predictions by Longuet-Higgins alongside Woodward and Hoffman; we also propose a simple phase space explanation for the appearance of the cyclopropyl photoionization spectrum. The results of this work allow the refinement of the cyclopropane C-H bond dissociation energy, in addition to the cyclopropyl radical and cation cyclization energies, via the Active Thermochemical Tables approach.

Atomic oxygen in its first excited singlet state, O(1 D), is an important species in the photochemistry of several planetary atmospheres and has been predicted to be a potentially important reactive species on interstellar ices. Here, we report the results of a kinetic study of the reactions of O(1 D) with methanol, CH3OH, and acetonitrile, CH3CN, over the 50-296 K temperature range. A continuous supersonic flow reactor was used to attain these low temperatures coupled with pulsed laser photolysis and pulsed laser induced fluorescence to generate and monitor O(1 D) atoms respectively. Secondary experiments examining the atomic hydrogen product channels of these reactions were also performed, through laser induced fluorescence measurements of H(2 S) atom formation. On the kinetics side, the rate constants for these reactions were seen to be large (> 2 x 10-10 cm 3 s-1) and consistent with barrierless reactions, although they display contrasting dependences as a function of temperature. On the product formation side, both reactions are seen to yield non-negligible quantities of atomic hydrogen. For the O(1 D) + CH3OH reaction, the derived yields are in good agreement with the conclusions of previous experimental and theoretical work. For the O(1 D) + CH3CN reaction, whose H-atom formation channels had not previously been investigated, electronic structure calculations of several new product formation channels were performed to explain the observed H-atom yields. These calculations demonstrate the barrierless and exothermic nature of the relevant exit channels, confirming that atomic hydrogen is also an important product of the O(1 D) + CH3CN reaction.

IntroductionDuring the only flyby of Triton by Voyager 2 in 1989, a dense ionosphere was observed (Tyler et al. 1989). Results were surprising as the solar irradiation of this satellite is ten times lower than on Titan, and yet its ionosphere is denser. Thus, electronic precipitation from Neptune’s magnetosphere was hypothesized to bring the needed extra input energy (Krasnopolsky et al. 1993), as high energy electrons have been observed by the spacecraft in this area (Krimigis et al. 1989). To understand how this precipitation could impact the composition of Triton’s atmosphere, we coupled an electron transport code to a photochemical model of this atmosphere.Methodology We used the electron transport code TRANS that was utilized to compute the transport of electrons in various planetary atmospheres (see Gronoff et al. 2009 and references therein). We adapted it to Triton’s conditions and used the results from Strobel et al. (1990) and Sittler and Hartle (1996) to compute the input precipitation. This led us to calculate the mean magnetic field and the mean precipitation before adjusting it depending on energy, as detailed in Sittler and Hartle (1996). We then coupled TRANS with our most recent photochemical model of Triton’s atmosphere (Benne et al. 2022) by using TRANS outputs to compute the reaction rates of the electro-dissociation and electro-ionization reactions. Iterations were performed between the two codes until steady state was reached. After determining the nominal composition of the atmosphere, we ran a Monte Carlo simulation to characterize the effect of chemical uncertainties on the model results.ResultsWith our previous model presented in Benne et al. (2022), we found a peak electronic number density larger by a factor of 2.5 to 5 compared to the one derived from Voyager 2 observations. By coupling the photochemical model with TRANS, we find that our electronic profile is now in agreement with these measurements, resulting from a significant decrease of the electro-ionization rate. In contrast with the results of Benne et al. (2022), Krasnopolsky and Cruikshank (1995) and Strobel and Summers (1995), the main ionization source is solar EUV radiation instead of magnetospheric electrons. This work also allows us to better understand how the varying magnetic environment impacts the atmospheric chemistry.References[1] Tyler, G. L. et al. Science 246, no. 4936 (December 15, 1989): 1466–73.[2] Krasnopolsky, V. A. et al. Journal of Geophysical Research 98 (February 1, 1993): 3065–78.[3] Krimigis, S. M. et al. Science 246, no. 4936 (December 15, 1989): 1483–89.[4] Gronoff, G. et al. Astronomy & Astrophysics 506, no. 2 (November 2009): 955–64.[5] Strobel, Darrell F. et al. Geophysical Research Letters 17, no. 10 (1990): 1661–64.[6] Sittler, E. C., and R. E. Hartle. Journal of Geophysical Research: Space Physics 101, no. A5 (May 1, 1996): 10863–76.[7] Benne, B. et al. Astronomy & Astrophysics 667 (November 2022): A169.[8] Krasnopolsky, Vladimir A., and Dale P. Cruikshank. Journal of Geophysical Research 100, no. E10 (1995): 21271.[9] Strobel, D. F., and M. E. Summers. 1995, 1107–48. Cruikshank, Dale P., Mildred Shapley Matthews, et A. M. Schumann. « Neptune and Triton », 1995.

The reaction between atomic carbon in its ground electronic state, C(3P), and nitrous oxide, N2O, has been studied below room temperature due to its potential importance for astrochemistry, with both species considered to be present at high abundance levels in a range of interstellar environments. On the experimental side, we measured rate constants for this reaction over the 50-296 K range using a continuous supersonic flow reactor. C(3P) atoms were generated by the pulsed photolysis of carbon tetrabromide at 266 nm and were detected by pulsed laser induced fluorescence at 115.8 nm. Additional measurements allowing the major product channels to be elucidated were also performed. On the theoretical side, statistical rate theory was used to calculate low temperature rate constants. These calculations employed the results of new electronic structure calculations of the 3A" potential energy surface of CNNO and provided a basis to extrapolate the measured rate constants to lower temperatures and pressures. The rate constant was found to increase monotonically as the temperature falls, reaching a value of k(C(3P)+N2O)(50 K) = (7.9 +- 0.8) x 10-11 cm3 s-1 at 50 K. As current astrochemical models do not include the C + N2O reaction, we tested the influence of this process on interstellar N2O and other related species using a gas-grain model of dense interstellar clouds. These simulations predict that N2O abundances decrease significantly at intermediate times (10^3 - 10^5 years) when gas-phase C(3P) abundances are high., Comment: Accepted for publication in the Journal of Physical Chemistry A

We report the mass-selected slow photoelectron spectra of three reactive organophosphorus species, PCH2, and the two isomers, methylenephosphine or phosphaethylene, HPCH2 and methylphosphinidine, P–CH3.

We report on a combined experimental and theoretical investigation of the N(2D) + C6H6 (benzene) reaction of relevance in the atmospheric chemistry of Titan. Experimentally, the reaction was studied (i)...

We report on a combined experimental and theoretical investigation of the N(

Atomic oxygen in its first excited singlet state, O(

Rate constants have been measured for the C(3P) + CH3CN reaction between 50 K and 296 K using a continuous-flow supersonic reactor. C(3P) atoms were created by the in-situ pulsed laser photolysis of CBr4 at 266 nm, while the kinetics of C(3P) atom loss were followed by direct vacuum ultra-violet laser induced fluorescence at 115.8 nm. Secondary measurements of product H(2S) atom formation were also made, allowing absolute H-atom yields to be obtained by comparison with those obtained for the C(3P) + C2H4 reference reaction. In parallel, quantum chemical calculations were performed to obtain the various complexes, adducts and transition states relevant to the title reaction over the triplet potential energy surface, allowing us to better understand the preferred reaction pathways. The reaction is seen to be very fast, with measured rate constants in the range (3-4) x 10-10 cm3 s-1 with little or no observed temperature dependence. As the C + CH3CN reaction is not considered in current astrochemical networks, we test its influence on interstellar methyl cyanide abundances using a gas-grain dense interstellar cloud model. Its inclusion leads to predicted CH3CN abundances that are significantly lower than the observed ones., Accepted in ACS Earth and Space Chemistry. 29 pages, 6 figures

We report the mass-selected slow photoelectron spectra of three reactive organophosphorus species, PCH

Triton is the largest satellite of Neptune and probably a Kuiper Belt Object that was captured by the planet. It has a tenuous nitrogen atmosphere similar to the one of Pluto and may be an ocean world. The Neptunian system has only been visited by Voyager 2 in 1989. Over the last few years, the demand for a new mission to the Ice Giants and their systems has increased so that a theoretical basis to prepare for such a mission is important. We aim to develop a photochemical model of Triton's atmosphere with an up-to-date chemical scheme, as previous photochemical models date back to the post-flyby years. This is done to better understand the mechanisms governing Triton's atmospheric chemistry and highlight the critical parameters having a significant impact on the atmospheric composition. We also study model uncertainties to find what chemical studies are necessary to improve the modeling of Triton's atmosphere. We adapted a model of Titan's atmosphere to Triton's conditions. We first used Titan's chemical scheme before updating it to better model Triton's atmosphere. Once the nominal results were obtained, we studied model uncertainties with a Monte-Carlo procedure. Then, we performed global sensitivity analyzes to identify the reactions responsible for model uncertainties. With the nominal results, we determined the composition of Triton's atmosphere and studied the main chemical processes. We highlighted key chemical reactions that are the most important for the overall chemistry. We also identified some key parameters having a significant impact on the results. Uncertainties are large for most of the main atmospheric species as the atmospheric temperature is very low. We identified key uncertainty reactions that have the largest impact on the results uncertainties. These reactions must be studied in priority in order to improve the significance of our results., Comment: 35 pages, 11 Figures, 7 Tables, 1 Appendix

Observational data of Titan's atmosphere composition, gathered in particular by the Cassini mission, allow accessing latitudinal, longitudinal and temporal variations of the altitudinal profiles of several species. While 1D models are a powerful tool to gain insight into the chemistry occurring in Titan's atmosphere, they cannot capture the four-dimensional nature of these processes at the same time. However, due to the large extent of the atmosphere and the complexity of chemistry, global 2D and 3D models with the chemical complexity of 1D models do not exist yet. On the way of developing a 2D photochemical model of Titan, including the very complex chemical schemes used in 1D models and also taking latitudinal variations into account, we developed an ultraviolet radiative transfer model to compute the actinic flux in a 2D geometry. We found that photolysis rates calculated in classical plane-parallel models to derive the rates in mean conditions give results notably different from a model that calculates the mean rates with a 2D geometry. We demonstrate that the introduction of the 2D geometry affects significantly the density profiles on both neutrals and ions, especially on nitriles. As a consequence, we advocate using radiative transfer model in 2D geometry from now on to interpret the wide diversity of observational data about Titan's atmosphere (pending the emergence of 2D models with complex chemical schemes).

Introduction Triton is the biggest satellite of Neptune. Discovered in 1846 by W. Lassell, it was visited by Voyager 2 in 1989. It was the only spacecraft to study the neptunian system. Very little was known about Triton at the time of the flyby, except its highly inclined retrograde orbit suggesting that it is a Kuiper Belt object captured by Neptune. This idea was also comforted by the similarities between Triton and Pluto. The flyby allowed to take high resolution pictures of the surface, to determine its temperature, pressure and the composition of the surface ices (N2, CH4, CO, CO2 and water ice). Clouds and haze were also observed respectively under 10 and 30km of altitude as well as plumes of organic material propagating up to 8km, pointing out the existence of a troposphere. It appeared that the low atmosphere was at vapor pressure equilibrium with the surface’s ices (Yelle et al. 1995). The atmosphere was also studied by measuring its airglow and by performing stellar occultations (Broadfoot et al. 1989). It revealed that it is mainly composed of N2, and N with traces of CH4 near the surface. CO was not detected and so only an upper limit on its abundance had been set. An important ionosphere was also observed with an important peak at 340km (Tyler and al. 1989). As Triton is far from the Sun, this important ionosphere cannot be explained by solar ionization only. So, it was hypothesized that energy was brought by precipitating electrons from the magnetosphere of Neptune (Strobel et al. 1990b). Another source of power is the interplanetary Lyman-Alpha flux that is not negligible at Triton’s distance from the Sun (Strobel et al. 1990a). However, since the Voyager 2 mission and its only flyby, Triton remains poorly understood in comparison to Titan which was intensely studied during the Cassini-Huygens mission (despite some observations with ALMA and the VLT, see Lellouch et al. 2010 and Merlin et al. 2018). And as for Titan, it is now supposed that Triton is an ocean world (Fletcher et al. 2020). Sending a new mission to the neptunian system appears as a necessity to increase our knowledge about ice giants and their systems. In order to prepare such a mission, having a theoretical photochemical model for Triton can be useful to have a reference against which we would compare data collected during such a mission. The photochemical model As a starting point, we used the photochemical model of Titan (see Dobrijevic et al. 2016) and adapted it to Triton. In particular, we used the chemical scheme developed for Titan (with recent updates presented in Hickson et al. 2020), as the two atmospheres are mainly composed of N2, with presence of CH4. Our methodology is presented on Figure 1. On Titan, CH4 is the second most abundant species but only traces were observed on Triton. Strobel et al. (1990a) suggested that this species was destructed by solar and interplanetary Lyman-Alpha radiation (as Triton is at 30 UA from the Sun, the interplanetary Ly-Alpha flux is comparable to the solar one). The atmosphere of Triton is also much less dense as the surface pressure is 14 bar against 1.5 bar on Titan. We use data from Strobel and Zhu (2017) for the initial temperature, pressure, density and eddy coefficient profiles. To obtain a first validation of our model, we compare our results with the Voyager 2 data and with the results presented in the principal articles about the photochemistry of Triton published after the Voyager 2 flyby: Strobel and Summers (1995), Krasnopolsky and Cruikshank (1995). Our model takes the interplanetary Ly-Alpha flux into account as well as the energy input of precipitating electrons from the neptunian magnetosphere by adding reactions of electron impact ionization and dissociation for N2. The ionization profile was taken from Strobel et al. (1990b). We modified the chemical network to adapt it to Triton’s atmospheric composition in order to get a nominal chemical scheme. The eddy coefficient profile is constrained to match our CH4 profile to the one measured by Voyager near the surface, as it was done in Strobel et al. (1990a) and Krasnopolsky and Cruikshank (1995). Our model takes actually into account 204 species (117 neutrals and 87 ions). Our chemical scheme is composed of 1570 reactions (154 photodissociations, 597 neutral reactions, 31 photoionizations and 788 ionic reactions). We use an altitudinal grid varying in H/5, H being the height scale of the atmosphere, giving 96 levels from 0 to 1026km. First results Our first results confirm that precipitation of magnetospheric electrons is very important to explain the composition of the ionosphere. The solar flux is also a critical parameter of the model since the CH4 abundance profile near the surface depends on the solar activity (the Voyager 2 flyby occurred near a solar maximum). This abundance profile also depends on the eddy diffusion coefficient. We also observed that the results depend strongly on some reactions. A study of the model’s uncertainties seems mandatory and will allow us to identify these key reactions. Uncertainties may indeed be large due to the low temperature of Triton’s atmosphere.

International audience; The photochemical processes at work in the atmosphere of Titan are very complex and lead to a great variety of compounds with aerosols as an end-product. One of the most complex molecules detected so far is benzene (C6H6). In the present work, we have updated and improved the chemistry of aromatics in order to better understand the main chemical pathways leading to the production of benzene and determine what other aromatics could be produced efficiently in the atmosphere. This new chemical scheme has been incorporated in our 1D photochemical model corresponding to mean conditions. We confirm the importance of ionic chemistry for benzene production in the upper atmosphere and we have found that excited benzene is an important intermediate in benzene production due to the exothermicity of many production reactions. Among the 24 aromatics included in the model, neutral aromatics like toluene (C6H5CH3) and ethylbenzene (C6H5C2H5) are relatively abundant, suggesting in particular that toluene could be detectable in the infrared, and eventually microwave wavelength ranges. However, we obtained large uncertainties on model results highlighting the need for more experiments and theoretical studies to improve the chemistry of aromatics.List of reactions (with rate constants) and references used in the present model.List of photodissociations and references used in the present model.For each reaction included in the model, the integrated column rate scaled to the surface (in cm-2 s-1) and the mean altitude (in km) of the production are given.In the three following files, we list the key reactions at 300 km, 500 km and 1000 km of altitude for all species in the present model.

International audience; Nitrogen Monoxide (NO) is observed in the gas phase of molecular clouds. It may accrete on dust grains and there its hydrogenation should lead to hydroxylamine (NH 2 OH), the same way that CO is transformed in methanol (CH 3 OH) on the surface dust grains. NO hydrogenation has been said barrier-less, whereas CO hydrogenation proceed through quantum tunneling, and is thus slower. However, CH 3 OH is widely observed and is considered as a proxy of complex organic molecules while hydroxy-lamine remains undetected. We aim at studying, analyzing, and understanding the 1 chemical network of NO hydrogenation on cold surfaces. Experiments are carried out using a new Ultra-Hight Vacuum (UHV) setup named VENUS. NO molecules and H atoms are co-deposited on a golden mirror at different temperatures. Infrared spectroscopy as well as Temperature Programmed Desorption (TPD) are used to follow the NO reactivity, with both H and D, and in presence or absence of water substrate. Quantum calculations on water ice cluster models are computed separately. During the hydrogenation of NO, 10 reactions proceed concurrently. They are identified and constrained by changing physical conditions in experiments or in calculations. Among them, we demonstrate that the HNO+H addition reaction has a barrier which is probably crossed via quantum tunneling at 10 K. Moreover, abstraction reactions are occurring although they are limited by H and O bonding with their environment. Chemical desorption should occur especially in absence of water which enhances the total production of hydroxylamine. The chemical network of the hydrogenation of NO has been re-investigated. Each of the 10 reactions are sorted by efficiency. We exclude the possibility of a chemical loop between NO and HNO, especially in presence of water. Therefore hydroxylamine remains the main product of the hydrogenation of NO on grains and the question of its non-detection in ices or in the gas phase, specifically in shocked regions where ice mantles should be sputtered, is still open.

The first measurement of the photoelectron spectrum of the silylidyne free radical, SiH, is reported between 7 and 10.5 eV. Two main photoionizing transitions involving the neutral ground state, X+1Σ+ ← X2Π and a+3Π ← X2Π, are assigned by using ab initio calculations. The corresponding adiabatic ionization energies are derived, IEad(X+1Σ+) = 7.934(5) eV and IEad(a+3Π) = 10.205(5) eV, in good agreement with our calculated values and the previous determination by Berkowitz et al. [J. Chem. Phys. 86, 1235 (1987)] from a photoionization mass spectrometric study. The photoion yield of SiH recorded in this work exhibits a dense autoionization landscape similar to that observed in the case of the CH free radical [Gans et al., J. Chem. Phys. 144, 204307 (2016)].

The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude ∠H1COH and ∠H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation–torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number K a due to the rotation–torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence.

28 pags., 22 figs., 4 tabs., Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30 m Large Program designed to provide estimates of the S, C, N, and O depletions and gas ionization degree, X(e−), in a selected set of star-forming filaments of Taurus, Perseus, and Orion. Our immediate goal is to build up a complete and large database of molecular abundances that can serve as an observational basis for estimating X(e−) and the C, O, N, and S depletions through chemical modeling. We observed and derived the abundances of 14 species (13CO, C18O, HCO+, H13CO+, HC18O+, HCN, H13CN, HNC, HCS+, CS, SO, 34SO, H2S, and OCS) in 244 positions, covering the AV ~3 to ~100 mag, n(H2) ~ a few 103 to 106 cm−3, and Tk ~10 to ~30 K ranges in these clouds, and avoiding protostars, HII regions, and bipolar outflows. A statistical analysis is carried out in order to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families of species: (1) 13CO and C18O isotopologs; (2) H13CO+, HC18O+, H13 CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature until TK ~ 15 K. For higher temperatures, the abundance remains constant with a scatter of a factor of ~3. The abundances of H13 CO+, HC18 O+, H13 CN, and HNC are well correlated with each other, and all of them decrease with molecular hydrogen density, following the law ∝ n(H2)−0.8 ± 0.2. The abundances of S-bearing species also decrease with molecular hydrogen density at a rate of (S-bearing/H)gas ∝ n(H2)−0.6 ± 0.1. The abundances of molecules belonging to groups 2 and 3 do not present any clear trend with gas temperature. At scales of molecular clouds, the C18O abundance is the quantity that better correlates with the cloud mass. We discuss the utility of the 13CO/C18O, HCO+/H13CO+, and H13 CO+/H13CN abundance ratios as chemical diagnostics of star formation in external galaxies., We thank the Spanish the Spanish Ministerio de Ciencia e Innovación for funding support through AYA2016-75066-C2-1/2-P and PID2019-106235GB-I00. SG-B acknowledges support through grants PGC2018-094671-B-I00 (MICIU/AEI/FEDER,UE) and PID2019-106027GAC44. JRG acknowledges support through grants AYA2017-85111-P and PID2019-106110GB-I00. I.J.-S. has received partial support from the Spanish FEDER (project number ESP2017-86582-C4-1-R) and the State Research Agency (AEI; project number PID2019-105552RB-C41). SPTM acknowledges to the European Union’s Horizon 2020 research and innovation program for funding support given under grant agreement No 639459 (PROMISE).

The NH

Aims: Interstellar molecules form early in the evolutionary sequence of interstellar material that eventually forms stars and planets. To understand this evolutionary sequence, it is important to characterize the chemical composition of its first steps. Methods: In this paper, we present the result of a 2 and 3 mm survey of five cold clumps identified by the Planck mission. We carried out a radiative transfer analysis on the detected lines in order to put some constraints on the physical conditions within the cores and on the molecular column densities. We also performed chemical models to reproduce the observed abundances in each source using the gas-grain model Nautilus. Results: Twelve molecules were detected: H2CO, CS, SO, NO, HNO, HCO+, HCN, HNC, CN, CCH, CH3OH, and CO. Here, CCH is the only carbon chain we detected in two sources. Radiative transfer analyses of HCN, SO, CS, and CO were performed to constrain the physical conditions of each cloud with limited success. The sources have a density larger than $10^4$ cm$^{-3}$ and a temperature lower than 15 K. The derived species column densities are not very sensitive to the uncertainties in the physical conditions, within a factor of 2. The different sources seem to present significant chemical differences with species abundances spreading over one order of magnitude. The chemical composition of these clumps is poorer than the one of Taurus Molecular Cloud 1 Cyanopolyyne Peak (TMC-1 CP) cold core. Our chemical model reproduces the observational abundances and upper limits for 79 to 83\% of the species in our sources. The "best" times for our sources seem to be smaller than those of TMC-1, indicating that our sources may be less evolved and explaining the smaller abundances and the numerous non-detections. Also, CS and HCN are always overestimated by our models., Accepted for publication in A&A

Complex organic molecules with three carbon atoms are found in the earliest stages of star formation. In particular, propenal (C$_2$H$_3$CHO) is a species of interest due to its implication in the formation of more complex species and even biotic molecules. This study aims to search for the presence of C$_2$H$_3$CHO and other three-carbon species such as propylene (C$_3$H$_6$) in the hot corino region of the low-mass protostellar binary IRAS 16293--2422 to understand their formation pathways. We use ALMA observations in Band 6 and 7 from various surveys to search for the presence of C$_3$H$_6$ and C$_2$H$_3$CHO towards the protostar IRAS 16293--2422 B (IRAS 16293B). We report the detection of both C$_3$H$_6$ and C$_2$H$_3$CHO towards IRAS 16293B, however, no unblended lines were found towards the other component of the binary system, IRAS 16293A. We derive column density upper limits for C$_3$H$_8$, HCCCHO, n-C$_3$H$_7$OH, i-C$_3$H$_7$OH, C$_3$O, and cis-HC(O)CHO towards IRAS 16293B. We then use a three-phase chemical model to simulate the formation of these species in a typical prestellar environment followed by its hydrodynamical collapse until the birth of the central protostar. Different formation paths, such as successive hydrogenation and radical-radical additions on grain surfaces, are tested and compared to the observational results. The simulations reproduce the abundances within one order of magnitude from those observed towards IRAS 16293B, with the best agreement found for a rate of $10^{-12}$ cm$^3$ s$^{-1}$ for the gas-phase reaction C$_3$ + O $\rightarrow$ C$_2$ + CO. Successive hydrogenations of C$_3$, HC(O)CHO, and CH$_3$OCHO on grain surfaces are a major and crucial formation route of complex organics molecules, whereas both successive hydrogenation pathways and radical-radical addition reactions contribute to the formation of C$_2$H$_5$CHO., Comment: Accepted for publication in A&A. 24 pages, 17 figures

9 pags., 6 figs., 2 tabs. -- Published as part of The Journal of Physical Chemistry virtual special issue “125 Years of The Journal of Physical Chemistry”., VUV photoionization of the CHnI radicals (with n = 0, 1, and 2) is investigated by means of synchrotron radiation coupled with a double imaging photoion-photoelectron coincidence spectrometer. Photoionization efficiencies and threshold photoelectron spectra (TPES) for photon energies ranging between 9.2 and 12.0 eV are reported. An adiabatic ionization energy (AIE) of 8.334 ± 0.005 eV is obtained for CH2I, which is in good agreement with previous results [8.333 ± 0.015 eV, Sztáray J. Chem. Phys. 2017, 147, 013944], while for CI an AIE of 8.374 ± 0.005 eV is measured for the first time and a value of ∼8.8 eV is estimated for CHI. Ab initio calculations have been carried out for the ground state of the CH2I radical and for the ground state and excited states of the radical cation CH2I+, including potential energy curves along the C–I coordinate. Franck–Condon factors are calculated for transitions from the CH2I(X̃2B1) ground state of the neutral radical to the ground state and excited states of the radical cation. The TPES measured for the CH2I radical shows several structures that correspond to the photoionization into excited states of the radical cation and are fully assigned on the basis of the calculations. The TPES obtained for the CHI is characterized by a broad structure peaking at 9.335 eV, which could be due to the photoionization from both the singlet and the triplet states and into one or more electronic states of the cation. A vibrational progression is clearly observed in the TPES for the CI radical and a frequency for the C–I stretching mode of 760 ± 60 cm–1 characterizing the CI+ electronic ground state has been extracted., D.V.C. acknowledges financial support from Spanish MINECO under the FPI predoctoral program. A.B. and A.G.V. acknowledge funding from the ICOOP program from CSIC (Grant COOPB20364), which made possible a research stay of A.B. at Instituto de Física Fundamental, CSIC. This work has been financed in part by the Spanish Ministry of Science and Innovation (Grant PGC2018-096444-B-I00) and has received financial support by French Agencie Nationale de la Recherche (ANR) under grant ANR-12-BS08-0020-02 (project SYNCHROKIN). The Centro de Supercomputación de Galicia (CESGA, Spain) and the Centro Técnico de Informática (CTI, CSIC) are acknowledged for the use of their resources.

International audience; The NH 2 radical is a key component in many astrophysical environments, both in its neutral and cationic forms, being involved in the formation of complex N-bearing species. To gain insight into the photochemical processes into which it operates and to model accurately the ensuing chemical networks, the knowledge of its photoionization efficiency is required, but no quantitative determination has been carried out so far. Combining a flow-tube H-abstraction radical source, a double imaging photoelectronphotoion spectrometer and a vacuum-ultraviolet synchrotron excitation, the absolute photoionization cross section of the amino radical has been measured in the present 1 work for the first time at two photon energies: σ NH 2 ion (12.7 eV) = 7.8 ± 2.2 Mb and σ NH 2 ion (13.2 eV) = 7.8 ± 2.0 Mb. These values have been employed to scale the total ion yield previously recorded by Gibson et al. (JCP, 83, pp 4319-4328 (1985)). The resulting cross section curve spanning the 11.1-15.7 eV energy range will help in refining the current astrophysical models.

Under cold conditions in dense cores, gas-phase molecules and atoms are depleted from the gas-phase to the surface of interstellar grains. Considering the time scales and physical conditions within these cores, a portion of these molecules has to be brought back into the gas-phase to explain their observation by milimeter telescopes. We tested the respective efficiencies of the different mechanisms commonly included in the models. We also tested the addition of sputtering of ice grain mantles via a collision with cosmic rays in the electronic stopping power regime. The ice sputtering induced by cosmic rays has been added to the Nautilus gas-grain model while the other processes were already present. Each of these processes were tested on a 1D physical structure determined by observations in TMC1 cold cores. The resulting 1D chemical structure was also compared to methanol gas-phase abundances observed in these cores. We found that all species are not sensitive in the same way to the non-thermal desorption mechanisms, and the sensitivity also depends on the physical conditions. Thus, it is mandatory to include all of them. Chemical desorption seems to be essential in reproducing the observations for H densities smaller than $4\times 10^4$~cm$^{-3}$, whereas sputtering is essential above this density. The models are, however, systematically below the observed methanol abundances. A more efficient chemical desorption and a more efficient sputtering could better reproduce the observations. In conclusion, the sputtering of ices by cosmic-rays collisions may be the most efficient desorption mechanism at high density (a few $10^4$~cm$^{-3}$ under the conditions studied here) in cold cores, whereas chemical desorption is still required at smaller densities. Additional works are needed on both mechanisms to assess their efficiency with respect to the main ice composition., Comment: Accepted for publication in A&A

Artículo escrito por un elevado número de autores, solo se referencia el que aparece en primer lugar, el nombre del grupo de colaboración, si lo hubiere, y los autores pertenecientes a la UAM, Context. Carbon monosulphide (CS) is among the most abundant gas-phase S-bearing molecules in cold dark molecular clouds. It is easily observable with several transitions in the millimeter wavelength range, and has been widely used as a tracer of the gas density in the interstellar medium in our Galaxy and external galaxies. However, chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur. Aims. The CS+O → CO + S reaction has been proposed as a relevant CS destruction mechanism at low temperatures, and could explain the discrepancy between models and observations. Its reaction rate has been experimentally measured at temperatures of 150-400 K, but the extrapolation to lower temperatures is doubtful. Our goal is to calculate the CS+O reaction rate at temperatures, The research leading to these results has received funding from MICIU (Spain) under grants FIS2017-83473-C2, AYA2016-75066- C2-2-P, ESP2017-86582-C4-1-R, AYA2017-85111-P, PID2019-105552RB-C41 and PID2019-106235GB-I00. N.B. acknowledges the computing facilities by TUBITAK-TRUBA, and O.R. and A.A. acknowledge computing time at Finisterre (CESGA) and Marenostrum (BSC) under RES computational grants ACCT-2019-3-0004 and AECT-2020-1-0003. SPTM acknowledges the European Union’s Horizon 2020 research and innovation program for funding support under agreement No 639459 (PROMISE)

The rates of numerous activated reactions between neutral species increase at low temperatures through quantum mechanical tunneling of light hydrogen atoms. Although tunneling processes involving molecules or heavy atoms are well known in the condensed phase, analogous gas-phase processes have never been demonstrated experimentally. Here, we studied the activated CH + CO

Context. The hydroxymethyl radical (CH2OH) is one of two structural isomers, together with the methoxy radical (CH3O), that can be produced by abstraction of a hydrogen atom from methanol (CH3OH). In the interstellar medium (ISM), both CH2OH and CH3O are suspected to be intermediate species in many chemical reactions, including those of formation and destruction of methanol. The determination of the CH3O/CH2OH ratio in the ISM would bring important information concerning the formation processes of these species in the gas and solid phases. Interestingly, only CH3O has been detected in the ISM so far, despite the recent first laboratory measurement of the CH2OH rotation-tunneling spectrum. This lack of detection is possibly due to the non-observation in the laboratory of the most intense rotation-tunneling transitions at low temperatures. Aims. To support further searches for the hydroxymethyl radical in space, we present a thorough spectroscopic study of its rotation-tunneling spectrum, with a particular focus on transitions involving the lowest quantum numbers of the species. Methods. We recorded the rotation-tunneling spectrum of CH2OH at room temperature in the millimeter-wave domain using a frequency multiplication chain spectrometer. A fluorine-induced H-abstraction method from methanol was used to produce the radical. Results. About 180 transitions were observed, including those involving the lowest N and Ka quantum numbers, which are predicted to be intense under cold astrophysical conditions. These transitions were fitted together with available millimeter-wave lines from the literature. A systematic observation of all components of the rotational transitions yields a large improvement of the spectroscopic parameters allowing confident searches of the hydroxymethyl radical in cold to warm environments of the ISM.

Carbon containing molecules in cold molecular clouds show various levels of isotopic fractionation through multiple observations. To understand such effects, we have developed a new gas-grain chemical model with updated 13C fractionation reactions (also including the corresponding reactions for 15N, 18O and 34S). For chemical ages typical of dense clouds, our nominal model leads to two 13C reservoirs: CO and the species that derive from CO, mainly s-CO and s-CH3OH, as well as C3 in the gas phase. The nominal model leads to strong enrichment in C3, c-C3H2 and C2H in contradiction with observations. When C3 reacts with oxygen atoms the global agreement between the various observations and the simulations is rather good showing variable 13C fractionation levels which are specific to each species. Alternatively, hydrogen atom reactions lead to notable relative 13C fractionation effects for the two non-equivalent isotopologues of C2H, c-C3H2 and C2S. As there are several important fractionation reactions, some carbon bearing species are enriched in 13C, particularly CO, depleting atomic 13C in the gas phase. This induces a 13C depletion in CH4 formed on grain surfaces, an effect that is not observed in the CH4 in the solar system, in particular on Titan. This seems to indicate a transformation of matter between the collapse of the molecular clouds, leading to the formation of the protostellar disc, and the formation of the planets. Or it means that the atomic carbon sticking to the grains reacts with the species already on the grains giving very little CH4., Accepted in MNRAS. 33 pages, 15 figures

The two isomers of the propylperoxy radical 1-C

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO

Measuring isotopic ratios is a sensitive technique used to obtain information on stellar nucleosynthesis and chemical evolution. We present measurements of the carbon and sulphur abundances in the interstellar medium of the central region of our Galaxy. The selected targets are the +50km/s Cloud and several l.o.s. clouds towards Sgr B2(N). Towards the +50km/s Cloud, we observed the J=2-1 rotational transitions of CS, C34S, 13CS, C33S, and 13C34S, and the J=3-2 transitions of CS and C34S with the IRAM-30m telescope, as well as the J=6-5 transitions of C34S and 13CS with the APEX 12m telescope, all in emission. The J=2-1 rotational transitions of CS, C34S, 13CS, and 13C34S were observed with ALMA in the envelope of Sgr B2(N), with those of CS and C34S also observed in the l.o.s. clouds towards Sgr B2(N), all in absorption. In the +50km/s Cloud we derive a 12C13C isotopic ratio of ~22.1, that leads, with the measured 13CS/C34S line intensity ratio, to a 32S/34S ratio of 16.3+3.0-2.4. We also derive the 32S/34S isotopic ratio more directly from the two isotopologues 13CS and 13C34S, which leads to an independent 32S/34S estimation of 16.3+2.1-1.7 and 17.9+-5.0 for the +50km/s Cloud and Sgr B2(N), respectively. We also obtain a 34S/33S ratio of ~4.3 in the +50 km/s Cloud. Previous studies observed a decreasing trend in the 32S/34S isotopic ratios when approaching the Galactic centre. Our result indicates a termination of this tendency at least at a galactocentric distance of 130-30+60 pc. This is at variance with findings based on 12C/13C, 14N/15N and 18O/17O isotope ratios, where the above-mentioned trend is observed to continue right to the central molecular zone. This can indicate a drop in the production of massive stars at the Galactic centre, in the same line as recent metallicity gradient studies, and opens the work towards a comparison with Galactic and stellar evolution models., Comment: 16 pages, 7 figures, accepted for publication by A&A

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO2), a key reaction intermediate in combustion and atmospheric chemistry as well as astrochemistry, using double imaging photoelectron photoion coincidence spectroscopy. The HO2 radical is formed in a microwave discharge flow tube reactor through a set of reactions initiated by F atoms in a CH4/O2/He gas mixture. The high-resolution threshold photoelectron spectrum of HO2 in the 11 eV–12 eV energy range is acquired without interferences from other species and assigned with the aid of theoretically calculated adiabatic ionization energies (AIEs) and Franck–Condon factors. The three vibrational modes of the radical cation HO2+, the H–O stretch, the H–O–O bend, and the O–O stretch, have been identified, and their individual frequencies are measured. In addition, the AIEs of the X3A″ ground state and the a1A′ first excited electronic state of HO2+ are experimentally determined at 11.359 ± 0.003 eV and 11.639 ± 0.005 eV, respectively, in agreement with high-level theoretically computed results. Furthermore, the former AIE value provides validation of thermochemical networks used to extract the enthalpy of formation of the HO2 radical.

We present here a synchrotron radiation vacuum ultraviolet photoionization study of the simplest alkoxy radical, CH3O, a key reaction intermediate in atmospheric and combustion chemistry. A microwave discharge fast flow tube connected to a molecular beam sampling system is employed as a chemical reactor to initiate reactions and generate radicals. The CH3O+ cation from direct ionization of the CH3O radical is detected successfully in the photoionization mass spectrum close to its ionization threshold. In addition, after identifying and removing the contribution of the 13C-isotopic formaldehyde H213CO with the same isobaric mass m/z = 31, the high-resolution threshold photoelectron spectrum of CH3O is obtained and assigned with the aid of calculated Franck–Condon factors. The adiabatic ionization energy of CH3O is determined at 10.701 eV with an accuracy of 0.005 eV. 153;3

Electronically excited nitrogen atoms N(

The photoelectron spectroscopy of CH2NC (isocyanomethyl) radical species is investigated for the first time between 9.3 and 11.2 eV in the vicinity of the first photoionizing transition X+1A1 ← X 2B1. The experiment combines a microwave discharge flow-tube reactor to produce the radicals through the CH3NC + F → CH2NC + HF reaction, a VUV synchrotron radiation excitation, and a double imaging electron/ion coincidence spectrometer which allows the recording of mass-selected threshold photoelectron spectra. Assignment of the observed vibrational structure of the CH2NC+ cation is guided by ab initio calculations and Franck-Condon simulations. From the experimental spectrum, the first adiabatic ionization energy of the CH2NC radical is measured as 9.439(6) eV. Fundamental wavenumbers are determined for several vibrational modes of the cation [small nu, Greek, tilde]1+(CH2 symmetric stretch) = 2999(80) cm-1, [small nu, Greek, tilde]2+(NC stretch) = 1925(40) cm-1, [small nu, Greek, tilde]4+(H2C-N stretch) = 1193(40) cm-1, [small nu, Greek, tilde]6+(CNC out-of-plane bend) = 237(50) cm-1, and [small nu, Greek, tilde]8+(CH2 rock) = 1185(60) cm-1.

The photoelectron spectroscopy of CH

21 pags., 16 figs., 7 tabs., 2 apps., Context. Sulphur is one of the most abundant elements in the Universe. Surprisingly, sulphuretted molecules are not as abundant as expected in the interstellar medium and the identity of the main sulphur reservoir is still an open question. Aims. Our goal is to investigate the H2S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir. Methods. Using millimeter observations of CS, SO, H2S, and their isotopologues, we determine the physical conditions and H2S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model NAUTILUS is used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H2S abundance. Results. Our modeling shows that chemical desorption is the main source of gas-phase H2S in dark cores. The measured H2S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when nH > 2 × 104. This change in the desorption rate is consistent with the formation of thick H2O and CO ice mantles on grain surfaces. The observed SO and H2S abundances are in good agreement with our predictions adopting an undepleted value of the sulphur abundance. However, the CS abundance is overestimated by a factor of 5-10. Along the three cores, atomic S is predicted to be the main sulphur reservoir. Conclusions. The gaseous H2S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H2S. The behavior of the observed H2S abundance suggests a changing desorption efficiency, which would probe the snowline in these cold cores. Our model, however, highly overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, we can only conclude that our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10., We thank the Spanish MINECO for funding support from AYA2016-75066-C2-1/2-P, AYA2017-85111P, and ERC under ERC-2013-SyG, G. A. 610256 NANOCOSMOS. JM acknowledges the support of ERC-2015-STG No. 679852 RADFEEDBACK. S.P.T.M. acknowledge to the European Union’s Horizon 2020 research and innovation program for funding support given under grant agreement No 639459 (PROMISE).

The vacuum ultraviolet (VUV) photoionization of the methyl peroxy radical, CH3O2, and unimolecular dissociation of internal energy selected CH3O2+ cations were investigated in the 9.7–12.0 eV energy range by synchrotron-based double imaging photoelectron photoion coincidence (i2PEPICO). A microwave discharge flow tube was employed to produce CH3O2 via the reaction of methyl radicals (CH3) with oxygen gas. After identifying and separating the different sources of CH3+ from photoionization of CH3 or dissociative photoionization of CH3O2, the high resolution slow photoelectron spectrum(SPES) of CH3O2 was obtained exhibiting two broad bands superimposed with a complex vibrational structure. The first band of the SPES is attributed to the X3A′′ and a1A′overlapped electronic states of CH3O2+ and the second is assigned to the b1A′ electronic state with the help of theoretical calculations. The adiabatic ionization energy (AIE) of CH3O2 is derived as 10.215 ± 0.015 eV, in good agreement with high-accuracytheoretical data from the literature. The vertical ionization energy of the b1A' electronic state is measured to be 11.5 eV and this state fully dissociates into CH3+ and O2fragments. The 0 K adiabatic appearance energy (AE0K) of the CH3+ fragment ion is determined to be 11.1548 ± 0.020 eV. 152;10