arXiv subjects

Valentine Wakelam

Publications and source records attributed to Valentine Wakelam.

At least 19 recordsLinked to original sources

arXiv2026

An ACA map of a molecular cloud interacting with supernova remnant W28

Supernova remnants (SNRs) strongly influence the physical and chemical properties of the molecular clouds (MCs) with which they interact. We carried out a high-resolution observation toward W28F, a chemically rich MC interacting with SNR W28, with the Atacama Compact Array (ACA) in Band 7. Significant emission (> 10 sigma) of CO, CH3OH, p-H2CO, SiO and SO is detected. We reveal the clumpy structures of the shocked MC, with different spatial distributions between CH3OH and SiO. We select six molecular clumps to conduct spectral decomposition and non-local-thermodynamic-equilibrium analysis with the CH3OH and p-H2CO lines. The best-fit results show a H2 density of nH2 ~ (1-3) * 10^5 cm^-3 and a gas temperature of Tgas ~ 50-170 K in most of the fitted components. The H2 density and gas temperature show a clear anti-correlation across different regions, with the thermal pressure consistent with that of the adjacent X-ray-emitting hot plasma. This is consistent with the picture that the SNR shocks propagate into multi-phase gas, with a pressure balance existing between different phases. We propose that the high abundance ratio between E-CH3OHand A-CH3OH (> 0.9) suggests extra gas-phase processes to enhance this ratio, such as proton exchange with H3+ and HCO+. The chemical segregation between CH3OH and SiO, in both the spatial and spectral regime, can be explained by the fact that CH3OH traces slow shocks while SiO traces fast shocks.

astro-ph.GA↗

arXiv2026

Simulation of proton radiolysis of H2O and O2 ices with the Nautilus code

The radiolysis effect of cosmic rays (CRs) plays an important role in the chemistry in molecular clouds. CRs can dissociate the molecules on dust grains, producing reactive suprathermal species and radicals which facilitate the formation of large molecules. We add the radiolysis process and some relevant reactions into the Nautilus astrochemical code. By adjusting some parameters, we investigate the sensitivity of the simulation results of the H2O ice on the removal of reaction-diffusion competition, the removal of non-diffusive chemistry, and the desorption energies of the suprathermal species. We find the model, with a few adjustments of the chemistry, can reproduce the steady-state [H2O2]/[H2O] and [O3]/[O2]_0 abundance ratios in the H2O and O2 radiolysis experiments at any CR flux in the experiments. These adjustments in the model do not fully reproduce the fluence required to reach the steady state. It tends also to overestimate the destruction of H2O as measured in H2O radiolysis experiments. We show that reducing the G-values of H2O radiolysis, which implies an increase in the efficiency of immediate reformation of water locally after ion impact, leads to simulated H2O destruction rates closer to the experiments. The effect of reaction-diffusion competition on the simulation results of H2O ice is significant at $\zeta \lesssim 10^{-14}\ \rm s^{-1}$. The non-diffusive chemistry affects the simulation results at 16 K but not 77K, while the results are sensitive to the desorption energies of suprathermal H, O, O3 and OH at 77 K. Our results show that the steady-state [H2O2]/[H2O] and [O3]/[O2]_0 in experiments can be reproduced by fine-tuning the chemical model, but still call for more constraints on the intermediate pathways in the radiolysis processes, especially the ion chemistry in the ice bulk, as well as activation barriers and branching ratios of the reactions in the network.

astro-ph.GA↗

arXiv2026

Using astrochemical models to simulate reactivity experiments on cold surfaces

The development of molecular complexity during stellar and planetary formation owes much to the interaction of gas and dust. When the first astrochemical models including solid-state chemistry were developed more than forty years ago, data from dedicated laboratory experiments were limited. Since then, many groups have developed specific experimental setups to address this issue, but astrochemical models have rarely been directly confronted with these new results. We want to demonstrate whether it is possible to use rate-equation-type astrochemical models developed in the context of the Interstellar Medium to compare them with laboratory astrophysics experiments. In this work, we use the case of low-temperature hydrogenation of CO, which is known to lead to methanol, among other molecules. We carried out 9 experiments, varying the experimental parameters such as temperature and dose. We give quantitative results and take care of detailing the vocabulary used in the experiments. We use astrochemical codes, NAUTILUS, pyRate and MONACO, to reproduce our experimental conditions, which requires good control of the change of vocabulary and scales, especially for fluxes and time scales. This work demonstrates that it is possible to use different astrochemical codes to compare modelling results directly with the output of experiments. There are discrepancies between models and experiments, as well as between models, but a fair agreement is achieved. We discuss the possible origin of the differences, which could originate from the chemical network or the difference in the description of physical processes.

astro-ph.GA↗

arXiv2025

The evolution of complex organic molecules during star formation

Complex organic molecules (COMs) are thought to be the precursors of pre-biotic molecules and are observed in many protostellar sources. For this paper we studied the formation of COMs during star formation and their evolution in the midplane of the circumstellar disk up to the end of the Class I stage. We used the Analytical Protostellar Environment (APE) code to perform analytical simulations of star formation and the Nautilus code to model the chemical evolution. Most COMs mainly form during the collapse or in the disk, except the lightest (CH3CCH, C3H6, CH3OH, CH3CHO, CH3OCH3, C2H5OH, CH3CN, CH3NC, C2H3CN, and CH3SH), which are significantly inherited by the disk from the prestellar phase. Over the first 150 kyr of the disk, the abundances of several COMs in the midplane vary negligibly (e.g., CH3CCH, CH3OH, and CH3CN), while others experience a variation of one order of magnitude (e.g., C2H3CHO HOCH2CHO, and CH3COCH2OH). Changing physical conditions also have an impact on the abundance profiles of COMs in the disk, and their inheritance. For example, increasing the temperature of the molecular cloud from 10 K to 15 K significantly promotes the formation of COMs in the prestellar phase, notably c-C2H4O and N-bearing species. Conversely, increasing the cloud mass from 2 Msol to 5 Msol only has a minor effect on the disk abundances in the early stages.

astro-ph.GA↗

arXiv2025

Rate constants and product yields for the C + CH3CHO reaction at low temperatures

Reactions involving atomic carbon in its ground electronic state, C(3P), play an important role in astrochemistry due to high C-atom abundance levels. Here we performed a kinetic investigation of the reaction between C(3P) and acetaldehyde, CH3CHO, determining rate constants for this process over the 50-296 K range. Measurements of the formation of atomic hydrogen, H(2S), were also performed to provide insight into product formation. Experiments were conducted using a supersonic flow reactor coupled with pulsed laser photolysis for C-atom generation and pulsed laser induced fluorescence in the vacuum ultraviolet range for the detection of both C(3P) and H(2S) atoms. Quantum chemical calculations of the ground triplet state potential energy surface of C3H4O were also performed to provide theoretical support for the measurements. The rate constants were large and temperature independent with an average value of 4.0 x 10-10 cm3 s-1. This result is consistent with the theoretical results which predict either very low barriers or none at all on the underlying potential energy surface. Although experimental difficulties prevented the quantitative determination of H-atom formation, qualitatively, H-atom yields were very low with CH3CH/C2H4 + CO as the major products based on the calculations. The influence of this reaction on interstellar chemistry was tested using a gas-grain model of dense interstellar clouds. These simulations predict that the C(3P) + CH3CHO reaction decreases gas-phase CH3CHO abundances by more than an order of magnitude at early and intermediate cloud ages, with a lower influence at typical dense cloud ages.

astro-ph.GA↗

arXiv2025

APE: An analytical protostellar environment to provide physical conditions to chemical models and synthetic observations

Chemical modeling and synthetic observations are powerful methods to interpret observations, both requiring a knowledge of the physical conditions. In this paper, we present the Analytical Protostellar Environment (APE) code, which aims at making chemical simulations and synthetic observations accessible. APE contains a physical model of protostellar evolution (including the central object, the envelope, the protoplanetary disk and the outflow) as well as interfaces to publicly available codes to perform chemical simulations, radiative transfer calculations, and synthetic interferometry imaging. APE produces density and temperature maps of protostellar systems. The code can also follow individual particles throughout their journey in a collapsing core. APE includes a treatment of the dust grain size-distribution to compute opacities self-consistently for subsequent radiative transfer. We show an example of application of APE by computing chemical abundance maps of CO, CN, CS, H2CO, and CH3OH in a Class I protostellar system. We also performed synthetic ALMA observations of their molecular emission assuming an edge-on source inclination. The moment 0 maps of CO, CS, and H2CO display an X-shaped emission similar to what is observed toward the Class I source IRAS 04302+2247.

astro-ph.SR↗

arXiv2025

Modelling methanol and hydride formation in the JWST Ice Age era

(Abridged) JWST observations have measured the ice composition toward two highly-extinguished field stars in the Chamaeleon I cloud. The observed extinction excess on the long-wavelength side of the H2O ice band at 3 micron has been attributed to a mixture of CH3OH with ammonia hydrates, which suggests that CH3OH ice could have formed in a water-rich environment with little CO depletion. Laboratory experiments and quantum chemical calculations suggest that CH3OH could form via the grain surface reactions CH3+OH and/or C+H2O in water-rich ices. However, no dedicated chemical modelling has been carried out thus far to test their efficiency and dependence on the astrochemical code employed. We model the ice chemistry in the Chamaeleon I cloud using a set of astrochemical codes (MAGICKAL, MONACO, Nautilus, UCLCHEM, and KMC simulations) to test the effects of the different code architectures and of the assumed ice chemistry. Our models show that the JWST ice observations are better reproduced for gas densities >1e5 cm-3 and collapse times >1e5 yr. CH3OH ice forms predominantly (>99%) via CO hydrogenation. The contribution of reactions CH3+OH and C+H2O, is negligible. The CO2 ice may form either via CO+OH or CO+O depending on the code. However, KMC simulations reveal that both mechanisms are efficient despite the low rate constant of the CO+O surface reaction. CH4 is largely underproduced for all codes except for UCLCHEM, for which a higher amount of atomic C is available during the initial translucent cloud phase. Large differences in the ice abundances are found at Tdust<12 K between diffusive and non-diffusive chemistry codes. This is due to the fact that non-diffusive chemistry takes over diffusive chemistry at such low Tdust. This could explain the rather constant ice chemical composition found in Chamaeleon I and other dense cores despite the different visual extinctions probed.

astro-ph.GA↗

arXiv2024

Molecular chemistry induced by J-shock toward supernova remnant W51C

Shock waves from supernova remnants (SNRs) have strong influence on the physical and chemical properties of molecular clouds (MCs). Shocks propagating into magnetized MCs can be classified into "jump" J-shock and "continuous" C-shock. The molecular chemistry in the re-formed molecular gas behind J-shock is still not well understood, which will provide a comprehensive view of the chemical feedback of SNRs and the chemical effects of J-shock. We conducted a W-band (71.4-89.7 GHz) observation toward a re-formed molecular clump behind a J-shock induced by SNR W51C with the Yebes 40 m radio telescope to study the molecular chemistry in the re-formed molecular gas. Based on the local thermodynamic equilibrium (LTE) assumption, we estimate the column densities of HCO+, HCN, C2H and o-c-C3H2, and derive the maps of their abundance ratios with CO. The gas density is constrained by non-LTE analysis of the HCO+ J=1-0 line. We obtain the following abundance ratios: $N({\rm HCO^+})/N({\rm CO})\sim (1.0\text{--}4.0)\times 10^{-4}$, $N({\rm HCN})/N({\rm CO})\sim (1.8\text{--}5.3)\times 10^{-4}$, $N({\rm C_2H})/N({\rm CO})\sim (1.6\text{--}5.0)\times 10^{-3}$, and $N({o\text{-}c\text{-}{\rm C_3H_2}})/N({\rm CO})\sim (1.2\text{--}7.9)\times 10^{-4}$. The non-LTE analysis suggests that the gas density is $n_{\rm H_2}\gtrsim 10^4\rm \ cm^{-3}$. We find that the N(C2H)/N(CO) and N(o-c-C3H2)/N(CO) are higher than typical values in quiescent MCs and shocked MCs by 1-2 orders of magnitude, which can be qualitatively attributed to the abundant C+ and C at the earliest phase of molecular gas re-formation. The Paris-Durham shock code can reproduce, although not perfectly, the observed abundance ratios, especially the enhanced N(C2H)/N(CO) and N(o-c-C3H2)/N(CO), with J-shocks propagating in to both non-irradiated and irradiated molecular gas with a preshock density of $n_{\rm H}=2\times 10^3\rm \ cm^{-3}$.

astro-ph.GA↗

arXiv2024

A Low Temperature Kinetic Study of the C(3P) + CH3OCH3 Reaction. Rate constants, H-atom Product Yields and Astrochemical Implications

Atomic carbon in its ground electronic state, C(3P), is expected to be present at high abundances during the evolution of dense molecular clouds. Consequently, its reactions with other interstellar species could have a strong influence on the chemical composition of these regions. Here, we report the results of an investigation of the reaction between C(3P) and dimethylether, CH3OCH3, which was recently detected in dark cloud TMC-1. Experiments were performed to study the kinetics of this reaction using a continuous supersonic flow reactor employing pulsed laser photolysis and pulsed laser induced fluorescence for atomic radical generation and detection respectively. Rate constants for this process were measured between 50 K and 296 K, while additional measurements of the product atomic hydrogen yields were also performed over the 75-296 K range. To better understand the experimental results, statistical rate theory was used to calculate rate constants over the same temperature range and to provide insight on the major product channels. These simulations, based on quantum chemical calculations of the ground triplet state of the C3H6O molecule, allowed us to obtain the most important features of the underlying potential energy surface. The measured rate constant increases as the temperature falls, reaching a value of k_(C+CH_3 OCH_3 )= 7.5 x 10-11 cm3 s-1 at 50 K, while the low measured H-atom yields support the theoretical prediction that the major reaction products are CH3 + CH3 + CO. The effects of this reaction on the abundances of interstellar CH3OCH3 and related species were tested using a gas-grain dense cloud model, employing an expression for the rate constant, k(T) = alpha(T/300)^beta, with alpha = 1.27 x 10-11 and beta = -1.01. These simulations predict that the C(3P) + CH3OCH3 reaction decreases gas-phase CH3OCH3 abundances by more than an order of magnitude at early times.

astro-ph.GA↗

arXiv2023

Kinetic Study of the Gas-Phase Reaction between Atomic Carbon and Acetone. Low Temperature Rate Constants and Hydrogen Atom Product Yields

The reactions of ground state atomic carbon, C(3P), are likely to be important in astrochemistry due to the high abundance levels of these atoms in the dense interstellar medium. Here we present a study of the gas-phase reaction between C(3P) and acetone, CH3COCH3. Experimentally, rate constants were measured for this process over the 50 to 296 K range using a continuous-flow supersonic reactor, while secondary measurements of H(2S) atom formation were also performed over the 75 to 296 K range to elucidate the preferred product channels. C(3P) atoms were generated by In-situ pulsed photolysis of carbon tetrabromide, while both C(3P) and H(2S) atoms were detected by pulsed laser induced fluorescence. Theoretically, quantum chemical calculations were performed to obtain the various complexes, adducts and transition states involved in the C(3P) + CH3COCH3 reaction over the 3A'' potential energy surface, allowing us to better understand the reaction pathways and help to interpret the experimental results. The derived rate constants are large, (2-3) x 10-10 cm3 s-1 , displaying only weak temperature variations; a result that is consistent with the barrierless nature of the reaction. As this reaction is not present in current astrochemical networks, its influence on simulated interstellar acetone abundances is tested using a gas-grain dense interstellar cloud model. For interstellar modelling purposes, the use of a temperature independent value for the rate constant, k(C+CH3COCH3 )= 2.2 x 10-10 cm3 s-1, is recommended. The C(3P) + CH3COCH3 reaction decreases gas-phase CH3COCH3 abundances by as much as two orders of magnitude at early and intermediate cloud ages.

astro-ph.GA↗

arXiv2023

Gas phase Elemental abundances in Molecular cloudS (GEMS) VIII. Unlocking the CS chemistry: the CH + S$\rightarrow$ CS + H and C$_2$ + S$\rightarrow$ CS + C reactions

We revise the rates of reactions CH + S -> CS + H and C_2 + S -> CS + C, important CS formation routes in dark and diffuse warm gas. We performed ab initio calculations to characterize the main features of all the electronic states correlating to the open shell reactants. For CH+S we have calculated the full potential energy surfaces for the lowest doublet states and the reaction rate constant with a quasi-classical method. For C_2+S, the reaction can only take place through the three lower triplet states, which all present deep insertion wells. A detailed study of the long-range interactions for these triplet states allowed to apply a statistic adiabatic method to determine the rate constants. This study of the CH + S reaction shows that its rate is nearly independent on the temperature in a range of 10-500 K with an almost constant value of 5.5 10^{-11} cm^3/s at temperatures above 100~K. This is a factor \sim 2-3 lower than the value obtained with the capture model. The rate of the reaction C_2 + S depends on the temperature taking values close to 2.0 10^{-10} cm^3/s at low temperatures and increasing to 5. 10^{-10} cm^3/s for temperatures higher than 200~K. Our modeling provides a rate higher than the one currently used by factor of \sim 2. These reactions were selected for involving open-shell species with many degenerate electronic states, and the results obtained in the present detailed calculations provide values which differ a factor of \sim 2-3 from the simpler classical capture method. We have updated the sulphur network with these new rates and compare our results in the prototypical case of TMC1 (CP). We find a reasonable agreement between model predictions and observations with a sulphur depletion factor of 20 relative to the sulphur cosmic abundance, but it is not possible to fit all sulphur-bearing molecules better than a factor of 10 at the same chemical time.

astro-ph.GA↗

arXiv2022

Investigating the hot molecular core, G10.47+0.03: A pit of nitrogen-bearing complex organic molecules

Recent observations have shown that Nitrogen-bearing complex organic species are present in large quantities in star-forming regions. Thus, investigating the N-bearing species in a hot molecular core, such as G10.47+0.03, is crucial to understanding the molecular complexity in star-forming regions. They also allow us to investigate the chemical and physical processes that determine the many phases during the structural and chemical evolution of the source in star-forming regions. The aim of this study is to investigate the spatial distribution and the chemical evolution states of N-bearing complex organic molecules in the hot core G10.47+0.03. We used the ALMA archival data of the hot molecular core G10.47+0.03. The extracted spectra were analyzed assuming LTE. Furthermore, robust methods such as MCMC and rotational diagram methods are implemented for molecules for which multiple transitions were identified to constrain the temperature and column density. Finally, we used the Nautilus gas-grain code to simulate the nitrogen chemistry in the hot molecular core. We carried out both 0D and 1D simulations of the source and compared with observational results. We report various transitions of nitrogen-bearing species (NH2CN, HC3N, HC5N, C2H3CN, C2H5CN, and H2NCH2CN) together with some of their isotopologues and isomers. Besides this, we also report the identification of CH3CCH and one of its isotopologues. The emissions originating from vinyl cyanide, ethyl cyanide, cyanoacetylene, and cyanamide are compact, which could be explained by our astrochemical modeling. Our 0D model shows that the chemistry of certain N-bearing molecules can be very sensitive to initial local conditions such as density or dust temperature. In our 1D model, simulated higher abundances of species such as HCN, HC3N, and HC5N toward the inner shells of the source confirm the observational findings.

astro-ph.GA↗

arXiv2022

AB Aur, a Rosetta stone for studies of planet formation (II): H$_2$S detection and sulfur budget

The sulfur abundance is poorly known in most environments. Yet, deriving the sulfur abundance is key to understanding the evolution of the chemistry from molecular clouds to planetary atmospheres. We present observations of H$_2$S 110-101 at 168.763 GHz toward the Herbig Ae star AB Aur. We aim to study the abundance of sulfuretted species toward AB Aur and to constrain how different species and phases contribute to the sulfur budget. We present new NOrthern Extended Millimeter Array (NOEMA) interferometric observations of the continuum and H$_2$S 110-101 line at 168.763 GHz toward AB Aur. We derived radial and azimuthal profiles and used them to compare the geometrical distribution of different species in the disk. Assuming local thermodynamical equilibrium (LTE), we derived column density and abundance maps for H$_2$S, and we further used Nautilus to produce a more detailed model of the chemical abundances at different heights over the mid-plane at a distance of r=200 au. We have resolved H$_2$S emission in the AB Aur protoplanetary disk. The emission comes from a ring extending from 0.67 (109 au) to 1.69 (275 au). Under simple assumptions, we derived an abundance of (3.1$\pm$0.8)$\times$10$\rm ^{-10}$ with respect to H nuclei, which we compare with Nautilus models to deepen our understanding of the sulfur chemistry in protoplanetary disks. Chemical models indicate that H$-2$S is an important sulfur carrier in the solid and gas phase. We also find an important transition at a height of 12 au, where the sulfur budget moves from being dominated by ice species to being dominated by gas species. Studying sulfuretted species in detail in the different phases of the interstellar medium is key to solving the issue.

astro-ph.SR↗

arXiv2022

The Si+SO$_2$ collision and an extended network of neutral-neutral reactions between silicon and sulphur bearing species

The Si+SO$_2$ reaction is investigated to verify its impact on the abundances of molecules with astrochemical interest, such as SiS, SiO, SO and others. According to our results Si($^3$P) and SO$_2$ react barrierlessly yielding only the monoxides SO and SiO as products. No favourable pathway has been found leading to other products, and this reaction should not contribute to SiS abundance. Furthermore, it is predicted that SiS is stable in collisions with O$_2$, and that S($^3$P)+SiO$_2$ and O($^3$P)+OSiS will also produce SO+SiO. Using these results and gathering further experimental and computational data from the literature, we provide an extended network of neutral-neutral reactions involving Si- and S-bearing molecules. The effects of these reactions were examined in a protostellar shock model, using the Nautilus gas-grain code. This consisted in simulating the physicochemical conditions of a shocked gas evolving from $i.$ primeval cold core, $ii.$ the shock region itself, $iii.$ and finally the gas bulk conditions after the passage of the shock. Emphasising on the cloud ages and including systematically these chemical reactions, we found that [SiS/H$_2$] can be of the order of $\sim$ 10$^{-8}$ in shocks that evolves from clouds of $t=1\times 10^6$ yr, whose values are mostly affected by the SiS+O $\longrightarrow$SiO+S reaction. Perspectives on further models along with observations are discussed in the context of sources harbouring molecular outflows.

astro-ph.GA↗

arXiv2022

An Experimental and Theoretical Investigation of the Gas-Phase C(3P) + N2O Reaction. Low Temperature Rate Constants and Astrochemical Implications

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.

astro-ph.GA↗

arXiv2022

Thermal desorption of interstellar ices. A review on the controlling parameters and their implications fromsnowlines to chemical complexity

The evolution of star-forming regions and their thermal balance are strongly influenced by their chemical composition, that, in turn, is determined by the physico-chemical processes that govern the transition between the gas phase and the solid state, specifically icy dust grains (e.g., particles adsorption and desorption). Gas-grain and grain-gas transitions as well as formation and sublimation of interstellar ices are thus essential elements of understanding astrophysical observations of cold environments (e.g., pre-stellar cores) where unexpected amounts of a large variety of chemical species have been observed in the gas phase. Adsorbed atoms and molecules also undergo chemical reactions which are not efficient in the gas phase. Therefore, the parameterization of the physical properties of atoms and molecules interacting with dust grain particles is clearly a key aspect to interpret astronomical observations and to build realistic and predictive astrochemical models. In this consensus evaluation, we focus on parameters controlling the thermal desorption of ices and how these determine pathways towards molecular complexity and define the location of snowlines, which ultimately influence the planet formation process. We review different crucial aspects of desorption parameters both from a theoretical and experimental point of view. We critically assess the desorption parameters commonly used in the astrochemical community for astrophysical relevant species and provide tables with recommended values. In addition, we show that a non-trivial determination of the pre-exponential factor nu using the Transition State Theory can affect the binding energy value. Finally, we conclude this work by discussing the limitations of theoretical and experimental approaches currently used to determine the desorption properties with suggestions for future improvements.

astro-ph.GA↗

arXiv2021

A kinetic study of the gas-phase C(3P) + CH3CN reaction at low temperature. Rate constants, H-atom product yields and astrochemical implications

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.

astro-ph.GA↗

arXiv2020

Chemical nitrogen fractionation in dense molecular clouds

Nitrogen-bearing molecules display variable isotopic fractionation levels in different astronomical environments such as in the interstellar medium or in the Solar System. Models of interstellar chemistry are unable to induce nitrogen fraction in cold molecular clouds as exchange reactions for 15N are mostly inefficient. Here, we developed a new gas-grain model for nitrogen fractionation including a thorough search for new nitrogen fractionation reactions and a realistic description of atom depletion onto interstellar dust particles. We show that, while dense molecular cloud gas-phase chemistry alone leads to very low fractionation, 14N atoms are preferentially depleted from the gas-phase due to a mass dependent grain surface sticking rate for atomic nitrogen. However, assuming an elementary 14N/15N ratio of 441 (equal to the solar wind value), our model leads to only low 15N enrichment for all N-containing species synthesized in the gas-phase with predicted 14N/15N ratios in the range 360-400. Higher enrichment levels can neither be explained by this mechanism, nor through chemistry, with two possible explanations. (I) The elementary 14N/15N ratio in the local ISM is smaller, as suggested by the recent work of Romano et al, with an hypothetic 15NNH+ and 15NNH+ depletion due to variation of the electronic recombination rate constant variation with the isotopes. (II) N2 photodissociation leads to variable nitrogen fractionation in diffuse molecular clouds where photons play an important role, which is conserved during dense molecular cloud formation as suggested by the work of Furuya & Aikawa.

astro-ph.GA↗