arXiv subjects

Michel Dobrijevic

Publications and source records attributed to Michel Dobrijevic.

13 recordsLinked to original sources

arXiv2025

A Gas-Phase Kinetic Study of the N(2D) + CH3CCH and N(2D) + CH3CN Reactions

The chemistry of planetary atmospheres containing molecular nitrogen as a major atmospheric component is strongly influenced by the reactions of atomic nitrogen. Although nitrogen atoms in their ground electronic state N(4S) are mostly unreactive towards stable molecules, electronically excited nitrogen atoms N(2D) are much more reactive and could play an important role in the formation of nitriles and other nitrogen bearing organic molecules in planetary atmospheres such as Titan. Despite this, few kinetic studies of N(2D) reactions have been performed over the appropriate low temperature range. Here, we report the results of an experimental study of the reactions N(2D) + methylacetylene, CH3CCH, and N(2D) + acetonitrile, CH3CN, using a supersonic flow reactor at selected temperatures between 50 K and 296 K. N(2D) atoms, which were generated indirectly as a product of the C(3P) + NO reaction, were subsequently detected by laser induced fluorescence in the vacuum ultraviolet wavelength region. The measured rate constants are significantly larger than the estimated values in current photochemical models and do not display large variations as a function of temperature. The new rate constants are included in a 1D coupled ion-neutral model of Titans atmosphere to test their influence on the simulated species abundances. In addition, the overall description of both reactions is improved by considering the results of recent experimental and theoretical work examining the product channels of these processes. These simulations indicate that while the N(2D) + CH3CCH reaction has only a limited overall influence on Titans atmospheric chemistry, the N(2D) + CH3CN reaction could lead to the formation of significant relative abundances of cyanomethamine, HNCHCN, in the upper atmosphere.

astro-ph.EP↗

arXiv2024

The Polar Stratosphere of Jupiter

Observations of the Jovian upper atmosphere at high latitudes in the UV, IR and mm/sub-mm all indicate that the chemical distributions and thermal structure are broadly influenced by auroral particle precipitations. Mid-IR and UV observations have shown that several light hydrocarbons (up to 6 carbon atoms) have altered abundances near Jupiter's main auroral ovals. Ion-neutral reactions influence the hydrocarbon chemistry, with light hydrocarbons produced in the upper stratosphere, and heavier hydrocarbons as well as aerosols produced in the lower stratosphere. One consequence of the magnetosphere-ionosphere coupling is the existence of ionospheric jets that propagate into the neutral middle stratosphere, likely acting as a dynamical barrier to the aurora-produced species. As the ionospheric jets and the background atmosphere do not co-rotate at the same rate, this creates a complex system where chemistry and dynamics are intertwined. The ion-neutral reactions produce species with a spatial distribution following the SIII longitude system in the upper stratosphere. As these species sediment down to the lower stratosphere, and because of the progressive dynamical decoupling between the ionospheric flows and the background atmosphere, the spatial distribution of the auroral-related species progressively follows a zonal distribution with increasing pressures that ultimately produces a system of polar and subpolar hazes that extends down to the bottom of the stratosphere. This paper reviews the most recent work addressing different aspects of this environment.

astro-ph.EP↗

arXiv2024

Evidence for auroral influence on Jupiter's nitrogen and oxygen chemistry revealed by ALMA

The localized delivery of new long-lived species to Jupiter's stratosphere by comet Shoemaker-Levy 9 in 1994 opened a window to constrain Jovian chemistry and dynamics by monitoring the evolution of their vertical and horizontal distributions. However, the spatial distributions of CO and HCN, two of these long-lived species, had never been jointly observed at high latitudinal resolution. Atacama large millimeter/submillimeter array observations of HCN and CO in March 2017 show that CO was meridionally uniform and restricted to pressures lower than 3 $\pm$ 1 mbar. HCN shared a similar vertical distribution in the low- to mid-latitudes, but was depleted at pressures between 2$^{+2}_ {-1}$ and 0.04$^{+0.07}_{-0.03}$ mbar in the aurora and surrounding regions, resulting in a drop by two orders of magnitude in column density. We propose that heterogeneous chemistry bonds HCN on large aurora-produced aerosols at these pressures in the Jovian auroral regions causing the observed depletion.

astro-ph.EP↗

arXiv2024

Low temperature formation of pyridine and (iso)quinoline via neutral neutral reactions

Aromatic molecules represent fundamental building blocks in prebiotic chemistry and are contemplated as vital precursors to DNA and RNA nitrogen bases. However, despite the identification of some 300 molecules in extraterrestrial environments, the pathways to pyridine (C5H5N), pyridinyl (C5H4N), and (iso)quinoline (C9H7N) the simplest representative of mono and bicyclic aromatic molecule carrying nitrogen are elusive. Here, we afford compelling evidence on the gas phase formation of methylene amidogen (H2CN) and cyanomethyl (H2CCN) radicals via molecular beam studies and electronic structure calculations. The modeling of the chemistries of Taurus Molecular Cloud (TMC 1) and Titans atmosphere contemplates a complex chain of reactions synthesizing pyridine, pyridinyl, and (iso)quinoline from H2CN and H2CCN at levels of up to 75%. This study affords unique entry points to precursors of DNA and RNA nitrogen bases in hydrocarbon rich extraterrestrial environments thus changing the way we think about the origin of prebiotic molecules in our Galaxy.

physics.chem-ph↗

arXiv2021

Science goals and new mission concepts for future exploration of Titan's atmosphere geology and habitability: Titan POlar Scout/orbitEr and In situ lake lander and DrONe explorer (POSEIDON)

In response to ESA Voyage 2050 announcement of opportunity, we propose an ambitious L-class mission to explore one of the most exciting bodies in the Solar System, Saturn largest moon Titan. Titan, a "world with two oceans", is an organic-rich body with interior-surface-atmosphere interactions that are comparable in complexity to the Earth. Titan is also one of the few places in the Solar System with habitability potential. Titan remarkable nature was only partly revealed by the Cassini-Huygens mission and still holds mysteries requiring a complete exploration using a variety of vehicles and instruments. The proposed mission concept POSEIDON (Titan POlar Scout/orbitEr and In situ lake lander DrONe explorer) would perform joint orbital and in situ investigations of Titan. It is designed to build on and exceed the scope and scientific/technological accomplishments of Cassini-Huygens, exploring Titan in ways that were not previously possible, in particular through full close-up and in situ coverage over long periods of time. In the proposed mission architecture, POSEIDON consists of two major elements: a spacecraft with a large set of instruments that would orbit Titan, preferably in a low-eccentricity polar orbit, and a suite of in situ investigation components, i.e. a lake lander, a "heavy" drone (possibly amphibious) and/or a fleet of mini-drones, dedicated to the exploration of the polar regions. The ideal arrival time at Titan would be slightly before the next northern Spring equinox (2039), as equinoxes are the most active periods to monitor still largely unknown atmospheric and surface seasonal changes. The exploration of Titan northern latitudes with an orbiter and in situ element(s) would be highly complementary with the upcoming NASA New Frontiers Dragonfly mission that will provide in situ exploration of Titan equatorial regions in the mid-2030s.

astro-ph.EP↗

arXiv2020

A Kinetic Study of the N(2D) + C2H4 Reaction at Low Temperature

Electronically excited nitrogen atoms N(2D) are important species in the photochemistry of N2 based planetary atmospheres such as Titan. Despite this, few N(2D) reactions have been studied over the appropriate low temperature range. During the present work, rate constants were measured for the N(2D) + ethene (C2H4) reaction using a supersonic flow reactor at temperatures between 50 K and 296 K. Here, a chemical reaction was used to generate N(2D) atoms, which were detected directly by laser induced fluorescence in the vacuum ultraviolet wavelength region. The measured rate constants displayed very little variation as a function of temperature, with substantially larger values than those obtained in previous work. Indeed, considering an average temperature of 170 K for the atmosphere of Titan leads to a rate constant that is almost seven times larger than the currently recommended value. In parallel, electronic structure calculations were performed to provide insight into the reactive process. While earlier theoretical work at a lower level predicted the presence of a barrier for the N(2D) + C2H4 reaction, the present calculations demonstrate that two of the five doublet potential energy surfaces correlating with reagents are likely to be attractive, presenting no barriers for the perpendicular approach of the N atom to the carbon double bond of ethene. The measured rate constants and new product channels taken from recent dynamical investigations of this process are included in a 1D coupled ion-neutral model of Titans atmosphere. These simulations indicate that the modeled abundances of numerous nitrogen bearing compounds are noticeably affected by these changes.

physics.chem-ph↗

arXiv2020

The deep composition of Uranus and Neptune from in situ exploration and thermochemical modeling

The distant ice giants of the Solar System, Uranus and Neptune, have only been visited by one space mission, Voyager 2. The current knowledge on their composition remains very limited despite some recent advances. A better characterization of their composition is however essential to constrain their formation and evolution, as a significant fraction of their mass is made of heavy elements, contrary to the gas giants Jupiter and Saturn. An in situ probe like Galileo would provide us with invaluable direct ground-truth composition measurements. However, some of the condensibles will remain out of the grasp of a shallow probe. While additional constraints could be obtained from a complementary orbiter, thermochemistry and diffusion modeling can further help us to increase the science return of an in situ probe.

astro-ph.EP↗

arXiv2019

A reduced chemical scheme for modelling warm to hot hydrogen-dominated atmospheres

Three dimensional models that account for chemistry are useful tools to predict the chemical composition of (exo)planet and brown dwarf atmospheres and interpret observations of future telescopes. Recent Juno observations of the NH3 tropospheric distribution in Jupiter also indicate that 3D chemical modelling may be necessary to constrain the deep composition of the giant planets of the Solar System. However, due to the high computational cost of chemistry calculations, 3D chemical modelling has so far been limited. A solution to include chemical kinetics in a 3D model is to use a reduced chemical scheme. In this view, we have developed a reduced scheme containing 30 species and 181 reversible reactions, from the full chemical scheme of Venot et al. 2012. This scheme reproduces accurately the vertical profiles of the observable species (H2O, CH4, CO, CO2, NH3, and HCN) and has a large range of validity. It can be used to study all kind of warm atmospheres, except hot C-rich ones, which contains a high amount of C2H2. It can be used in 1D models, for fast computations, but also in 3D models for hot giant (exo)planet and brown dwarf atmospheres.

astro-ph.EP↗

arXiv2018

Photochemistry, mixing and transport in Jupiter's stratosphere constrained by Cassini

We aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere. The IR spectrum recorded by Cassini/CIRS during the Jupiter flyby contains the fingerprints of several atmospheric compounds and allows probing its atmospheric composition. C2H2 and C2H6, the main compounds produced by methane photochemistry, were retrieved as a function of latitude at certain pressure levels. CIRS observations suggest a different meridional distribution for these two species, difficult to reconcile with their photochemical histories, which are thought to be coupled to the methane photolysis. While the C2H2 abundance decreases with latitude, C2H6 becomes more abundant at high latitudes. A new 2D (latitude-altitude) seasonal photochemical model is developed to study whether the addition of stratospheric transport processes, such as meridional diffusion and advection, can explain the latitudinal behavior of C2H2 and C2H6. C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, but degrades the fit to the C2H2 distribution. Meridional diffusion alone cannot produce the observed increase with latitude of C2H6. When adding advective transport between 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can reproduce the C2H6 abundance increase with latitude. However, the fit to the C2H2 distribution is degraded. The strength of the advective winds needed to reproduce the C2H6 abundances is very sensitive to the value of the meridional eddy diffusion coefficient. The coupled fate of C2H2 and C2H6 suggests that an additional process is missing in the model. Ion-neutral chemistry was not accounted for in this work and might be a good candidate to solve this issue.

astro-ph.EP↗

arXiv2015

2D photochemical modeling of Saturn's stratosphere. Part I: Seasonal variation of atmospheric composition without meridional transport

Saturn's axial tilt of 26.7° produces seasons in a similar way as on Earth. Both the stratospheric temperature and composition are affected by this latitudinally varying insolation along Saturn's orbital path. A new time dependent 2D photochemical model is presented to study the seasonal evolution of Saturn's stratospheric composition. This study focuses on the impact of the seasonally variable thermal field on the main stratospheric C2 hydrocarbon chemistry (C2H2 and C2H6) using a realistic radiative climate model. Meridional mixing and advective processes are implemented in the model but turned off in the present study for the sake of simplicity. The results are compared to a simple study case where a latitudinally and temporally steady thermal field is assumed. Our simulations suggest that, when the seasonally variable thermal field is accounted for, the downward diffusion of the seasonally produced hydrocarbons is faster due to the seasonal compression of the atmospheric column during winter. This effect increases with increasing latitudes which experience the most important thermal changes in the course of the seasons. The seasonal variability of C2H2 and C2H6 therefore persists at higher-pressure levels with a seasonally-variable thermal field. Cassini limb-observations of C2H2 and C2H6 (Guerlet et al., 2009) are reasonably well-reproduced from the equator to 40° in both hemispheres

astro-ph.EP↗

arXiv2015

VUV-absorption cross section of CO2 at high temperatures and impact on exoplanet atmospheres

Ultraviolet (UV) absorption cross sections are an essential ingredient of photochemical atmosphere models. Exoplanet searches have unveiled a large population of short-period objects with hot atmospheres, very different from what we find in our solar system. Transiting exoplanets whose atmospheres can now be studied by transit spectroscopy receive extremely strong UV fluxes and have typical temperatures ranging from 400 to 2500 K. At these temperatures, UV photolysis cross section data are severely lacking. Our goal is to provide high-temperature absorption cross sections and their temperature dependency for important atmospheric compounds. This study is dedicated to CO2, which is observed and photodissociated in exoplanet atmospheres. We performed these measurements for the 115 - 200 nm range at 300, 410, 480, and 550 K. In the 195 - 230 nm range, we worked at seven temperatures between 465 and 800 K. We found that the absorption cross section of CO2 is very sensitive to temperature, especially above 160 nm. Within the studied range of temperature, the CO2 cross section can vary by more than two orders of magnitude. This, in particular, makes the absorption of CO2 significant up to wavelengths as high as 230 nm, while it is negligible above 200 nm at 300 K. To investigate the influence of these new data on the photochemistry of exoplanets, we implemented the measured cross section into a 1D photochemical model. The model predicts that accounting for this temperature dependency of CO2 cross section can affect the computed abundances of NH3, CO2, and CO by one order of magnitude in the atmospheres of hot Jupiter and hot Neptune.

astro-ph.EP↗

arXiv2013

High-temperature measurements of VUV-absorption cross sections of CO2 and their application to exoplanets

UV absorption cross sections are an essential ingredient of photochemical atmosphere models. Exoplanet searches have unveiled a large population of short-period objects with hot atmospheres, very different from what we find in our solar system. Transiting exoplanets whose atmospheres can now be studied by transit spectroscopy receive extremely strong UV fluxes and have typical temperatures ranging from 400 to 2500 K. At these temperatures, UV photolysis cross section data are severely lacking. Aims. Our goal is to provide high-temperature absorption cross sections and their temperature dependency for important atmospheric compounds. This study is dedicated to CO2, which is observed and photodissociated in exoplanet atmospheres. We also investigate the influence of these new data on the photochemistry of some exoplanets. We performed these measurements for the 115 - 200 nm range at 300, 410, 480, and 550 K. In the 195 - 230 nm range, we worked at seven temperatures between 465 and 800 K. We implemented the measured cross section into a 1D photochemical model. For wavelengths > 170 nm, the wavelength dependence of ln(cross-section_CO2(wavelength, T)x1/Qv(T)) can be parametrized with a linear law. Thus, we can interpolate cross-section_CO2(wavelength, T) at any temperature between 300 and 800 K. Within the studied range of temperature, the CO2 cross section can vary by more than two orders of magnitude. This, in particular, makes the absorption of CO2 significant up to wavelengths as high as 230 nm. The absorption cross section of CO2 is very sensitive to temperature. The model predicts that accounting for this temperature dependency of CO2 cross section can affect the computed abundances of NH3, CO2, and CO by one order of magnitude in the atmospheres of hot Jupiter and hot Neptune. This effect will be more important in hot CO2-dominated atmospheres.

astro-ph.EP↗

arXiv2012

A chemical model for the atmosphere of hot Jupiters

Our purpose is to release a chemical network, and the associated rate coefficients, developed for the temperature and pressure range relevant to hot Jupiters atmospheres. Using this network, we study the vertical atmospheric composition of the two hot Jupiters (HD209458b, HD189733b) with a model that includes photolyses and vertical mixing and we produce synthetic spectra. The chemical scheme is derived from applied combustion models that have been methodically validated over a range of temperatures and pressures typical of the atmospheric layers influencing the observations of hot Jupiters. We compare the predictions obtained from this scheme with equilibrium calculations, with different schemes available in the literature that contain N-bearing species and with previously published photochemical models. Compared to other chemical schemes that were not subjected to the same systematic validation, we find significant differences whenever non-equilibrium processes take place. The deviations from the equilibrium, and thus the sensitivity to the network, are more important for HD189733b, as we assume a cooler atmosphere than for HD209458b. We found that the abundances of NH3 and HCN can vary by two orders of magnitude depending on the network, demonstrating the importance of comprehensive experimental validation. A spectral feature of NH3 at 10.5$μ$m is sensitive to these abundance variations and thus to the chemical scheme. Due to the influence of the kinetics, we recommend the use of a validated scheme to model the chemistry of exoplanet atmospheres. Our network is robust for temperatures within 300-2500K and pressures from 10mbar up to a few hundreds of bars, for species made of C,H,O,N. It is validated for species up to 2 carbon atoms and for the main nitrogen species.

astro-ph.EP↗