arXiv subjects

Benjamin Fleury

Publications and source records attributed to Benjamin Fleury.

13 recordsLinked to original sources

arXiv2025

High-temperature measurements of acetylene VUV absorption cross sections and application to warm exoplanet atmospheres

Most observed exoplanets have high equilibrium temperatures. Understanding the chemistry of their atmospheres and interpreting their observations requires the use of chemical kinetic models including photochemistry. The thermal dependence of the vacuum ultraviolet (VUV) absorption cross sections of molecules used in these models is poorly known at high temperatures, leading to uncertainties in the resulting abundance profiles. The aim of our work is to study experimentally the thermal dependence of VUV absorption cross sections of molecules of interest for exoplanet atmospheres and provide accurate data for use in atmospheric models. This study focuses on acetylene (C2H2). We measured absorption cross sections of C2H2 at seven temperatures ranging from 296 to 773 K recorded in the 115-230 nm spectral domain using VUV spectroscopy and synchrotron radiation. These data were used in our 1D thermo-photochemical model, to assess their impact on the predicted composition of a generic hot Jupiter-like exoplanet atmosphere. The absolute absorption cross sections of C2H2 increase with temperature. This increase is relatively constant from 115 to 185 nm and rises sharply from 185 to 230 nm. The abundance profile of C2H2 calculated using the model shows a slight variation, with a maximum decrease of 40% near 5 x 10-5 bar, when using C2H2 absorption cross sections measured at 773 K compared to those at 296 K. This is explained by the absorption, higher in the atmosphere, of the actinic flux from 150 to 230 nm due to the increase in the C2H2 absorption in this spectral range. This change also impacts the abundance profiles of other by-products such as methane (CH4) and ethylene (C2H4). We present the first experimental measurements of the VUV absorption cross sections of C2H2 at high temperatures. Similar studies of other major species are needed to improve our understanding of exoplanet atmospheres.

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arXiv2024

Experimental investigations of diacetylene ice photochemistry in Titan's atmospheric conditions

A large fraction of the organic species produced photochemically in the atmosphere of Titan can condense to form ice particles in the stratosphere and in the troposphere. According to various studies, diacetylene (C$_4$H$_2$) condenses below 100 km where it can be exposed to ultraviolet radiation. We studied experimentally the photochemistry of diacetylene ice (C$_4$H$_2$) to evaluate its potential role in the lower altitude photochemistry of Titan's atmospheric ices. Methods. C$_4$H$_2$ ice films were irradiated with near-ultraviolet (near-UV) photons ( {\lambda} > 300 nm) with different UV sources to assess the impact of the wavelengths of photons on the photochemistry of C$_4$H$_2$. The evolution of the ice's composition was monitored using spectroscopic techniques. Our results reveal that diacetylene ice is reactive through singlet-triplet absorption, similar to the photochemistry of other organic ices of Titan (such as dicyanoacetylene C$_4$N$_2$ ice) that we investigated previously. Several chemical processes occurred during the photolysis: the hydrogenation of C$_4$H$_2$ to form other C$_4$ hydrocarbons (vinylacetylene C$_4$H$_4$ to butane C$_4$H$_{10}$); the formation of larger and highly polymerizable hydrocarbons, such as triacetylene (C$_6$H$_2$); and the formation of an organic polymer that is stable at room temperature. The nondetection of diacetylene ice in Titan's atmosphere or surface could be rationalized based on our experimental results that C$_4$H$_2$ is photochemically highly reactive in the solid phase when exposed to near-UV radiation that reaches Titan's lower altitudes and surface. C$_4$H$_2$ may be one of the key molecules promoting the chemistry in the ices and aerosols of Titan's haze layers, especially in the case of co-condensation with other organic volatiles, with which it could initiate more complex solid-phase chemistry.

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arXiv2023

Experimental Investigation of the Photochemical Production of Hydrocarbons in Warm Gas Giant Exoplanet Atmospheres

In warm (equilibrium temperature <1000 K) gas giant exoplanet atmospheres, the observation of trace species in abundances deviating from thermochemical equilibrium predictions could be used as an indicator of disequilibrium chemical processes, such as photochemistry. To predict which compounds could be used as such tracers, it is therefore essential to study how photochemical processes affect their abundances. For this purpose, we investigated experimentally the efficiency of the photochemical formation of hydrocarbons in gas mixtures representative of warm gas giant atmospheres as a function of the gas temperature at millibar pressures. We find that, compared to thermal reactions alone, photochemistry efficiently promotes, under the studied conditions, the formation of hydrocarbons, with the detection of acetylene, ethane, and propane, as well as carbon monoxide. Therefore, our results confirm the importance of photochemistry in exoplanet atmospheres as a disequilibrium process. Ethane is the major hydrocarbon formed in our experiments, in apparent contradiction with the prediction by thermophotochemical models that acetylene should be the main hydrocarbon product. We also observe an evolution of the hydrocarbon production efficiency as a function of the temperature, a behavior not reproduced by a 0D thermophotochemical model. Additional studies are necessary to definitively understand the origin of the differences between the experimental and modeling results and to infer the importance of our results for understanding hydrocarbon formation in warm gas giant exoplanet atmospheres. Finally, our work demonstrates the importance of experimental studies together with modeling studies to accurately interpret, understand, and predict observations of exoplanet atmospheres.

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arXiv2023

Thermal Behavior of Astrophysical Amorphous Molecular Ices

Ice is a major component of astrophysical environment - from interstellar molecular clouds through protoplanetary disks to evolved solar systems. Ice and complex organic matter coexist in these environments as well, and it is thought primordial ice brought the molecules of life to Earth four billion years ago, which could have kickstarted the origin of life on Earth. To understand the journey of ice and organics from their origins to becoming a part of evolved planetary systems, it is important to complement high spatial and spectral resolution telescopes such as JWST with laboratory experimental studies that provide deeper insight into the processes that occur in these astrophysical environments. Our laboratory studies are aimed at providing this knowledge. In this article we present simultaneous mass spectrometric and infrared spectroscopic investigation on how molecular ice mixtures behave at different temperatures and how this information is critical to interpret observational data from protoplanetary disks as well as comets. We find that amorphous to crystalline water ice transformation is the most critical phenomenon that differentiates between outgassing of trapped volatiles such as CO2 vs. outgassing of pure molecular ice domains of the same in a mixed molecular ice. Crystalline water ice is found to trap only a small fraction of other volatiles (<5%), indicating ice grain composition in astrophysical and planetary environments must be different depending on whether the ice is in amorphous phase or transformed into crystalline phase, even if the crystalline ice undergoes radiation-induced amorphization subsequently. Crystallization of water ice is a key differentiator for many ices in astronomical environments as well as in our Solar System.

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arXiv2023

High-fidelity reaction kinetic modeling of hot-Jupiter atmospheres incorporating thermal and UV photochemistry enhanced by metastable CO(a3Pi)

A detailed modeling of simultaneous UV-photochemical and thermochemical processes in exoplanet atmosphere-like conditions is essential for the analysis and interpretation of a vast amount of current and future spectral data from exoplanets. However, a detailed reaction kinetic model that incorporates both UV photochemistry and thermal chemistry is challenging due to the massive size of the chemical system as well as to the lack of understanding of photochemistry compared to thermal-only chemistry. Here, we utilize an automatic chemical reaction mechanism generator to build a high-fidelity thermochemical reaction kinetic model later then incorporated with UV-photochemistry enhanced by metastable triplet-state carbon monoxide (a3Pi). Our model results show that two different photochemical reactions driven by Lyman-a photons (i.e. H2 + CO(a3Pi) -> H + HCO and CO(X1Sig+) + CO(a3Pi) -> C(3P) + CO2) can enhance thermal chemistry resulting in significant increases in the formation of CH4, H2O, and CO2 in H2-dominated systems with trace amounts of CO, which qualitatively matches with the observations from previous experimental studies. Our model also suggests that at temperatures above 2000 K, thermal chemistry becomes the dominant process. Finally, the chemistry simulated up to 2500 K does not produce any larger species such as C3 species, benzene or larger (i.e. PAHs). This might indicate that the photochemistry of C2 species such as C2H2 might play a key role in the formation of organic aerosols observed in the previous experimental study.

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arXiv2022

Influence of C/O Ratio on Hot Jupiter Atmospheric Chemistry

We have conducted laboratory experiments to study the chemistry in hot Jupiter atmospheres with C/O ratio of 0.35. We have compared our results with the ones obtained previously for atmospheres with a C/O ratio of 1 to investigate the influence of the C/O ratio on the chemistry and formation of photochemical organic aerosol. We found that the C/O ratio and the gas mixture compositions strongly influence the pathways responsible for the formation of CO2. Thermochemical reactions are primarily responsible for the formation of CO2 in low C/O ratio atmospheres, while photochemistry is the dominant process in high C/O ratio atmospheres even if the final CO2 concentration is the same in both cases. Our results show that low C/O atmospheres at the thermochemical equilibrium contain a higher water abundance, while high C/O atmospheres are significantly depleted in water. However, in low C/O atmospheres, the water abundance is not affected by UV photolysis, while our previous work demonstrated that significant amount of water can be produced in high C/O ratio atmospheres. This contrast in water production suggests that photochemistry should be considered when interpreting exoplanet transit spectra. Finally, we did not observe the formation of a detectable amount of non-volatile photochemical aerosols in low C/O atmospheres, in contrast to our previous study. We infer that for C/O ratio < 1, water likely inhibits organic growth and aerosol formation, suggesting that photochemical organic aerosols are likely to be observed in planets presenting a carbon enrichment compared to their host stars.

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arXiv2022

Photochemistry in hot H2-dominated exoplanet atmospheres

Photochemistry has the potential to substantially impact the atmospheric composition of exoplanets with consequences on the radiative transfer, thermal structure and dynamics of the atmospheres, particularly in UV-rich stellar environments. Here, we present the results of a first laboratory experimental simulation of photochemistry in carbon-rich exoplanet atmospheres at elevated temperatures. Evolution of gas-phase molecular composition was quantitatively monitored with infrared spectroscopy and mass spectrometry. We found that H2/CO gas compositions can change significantly from thermal equilibria compositions when irradiated with Lyman-alpha photons at temperatures ranging from 600 K to 1500 K. Carbon dioxide and water were found to be the main products caused by photolysis, while formation of methane was also observed to a lesser extent. We find that photochemistry efficiency is strongly correlated with increasing temperature. Our finding that water is efficiently produced by photochemistry in a super Solar C/O=1 environment, representing C enhancement relative to solar values C/O ratio = 0.54, has significant implications for the interpretation of many exoplanet transmission spectra. We also find the formation of an organic solid condensate at 1500 K and under Lyman-alpha UV-radiation, confirming the possibility of forming photochemical hazes in hot-Jupiter exoplanet atmospheres with an enhanced C/O ratio compared to Solar.

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arXiv2020

The Importance of Prioritizing Exoplanet Experimental Facilities

Continuous improvements of observations and modeling efforts have led to tremendous strides in exoplanetary science. However, as instruments and techniques advance laboratory data becomes more important to interpret exoplanet observations and verify theoretical modeling. Though experimental studies are often deferred due to their high costs and long timelines, it is imperative that laboratory investigations are prioritized to ensure steady advances in the field of exoplanetary science. This White Paper discusses the importance of prioritizing exoplanetary laboratory efforts, and discusses several experimental facilities currently performing exoplanetary research.

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arXiv2019

The Need for Laboratory Measurements and Ab Initio Studies to Aid Understanding of Exoplanetary Atmospheres

We are now on a clear trajectory for improvements in exoplanet observations that will revolutionize our ability to characterize their atmospheric structure, composition, and circulation, from gas giants to rocky planets. However, exoplanet atmospheric models capable of interpreting the upcoming observations are often limited by insufficiencies in the laboratory and theoretical data that serve as critical inputs to atmospheric physical and chemical tools. Here we provide an up-to-date and condensed description of areas where laboratory and/or ab initio investigations could fill critical gaps in our ability to model exoplanet atmospheric opacities, clouds, and chemistry, building off a larger 2016 white paper, and endorsed by the NAS Exoplanet Science Strategy report. Now is the ideal time for progress in these areas, but this progress requires better access to, understanding of, and training in the production of spectroscopic data as well as a better insight into chemical reaction kinetics both thermal and radiation-induced at a broad range of temperatures. Given that most published efforts have emphasized relatively Earth-like conditions, we can expect significant and enlightening discoveries as emphasis moves to the exotic atmospheres of exoplanets.

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arXiv2019

Photoreactivity of condensed acetylene on Titan aerosols analogues

Volatile organic molecules formed by photochemistry in the upper atmosphere of Titan can undergo condensation as pure ices in the stratosphere and the troposphere as well as condense as ice layers onto the organic aerosols that are visible as the haze layers of Titan. As solar photons penetrate through Titan s atmosphere, shorter-wavelength photons are attenuated and longerwavelength photons make it into the lower altitudes, where aerosols become abundant. We conducted an experimental study to evaluate the long wavelength ( > 300 nm) photo-reactivity of these ices accreted on the Titan aerosol-analogs (also known as tholins) made in the laboratory. We have focused on acetylene, the third most abundant hydrocarbon in Titan s atmosphere after CH4 and C2H6. Further, acetylene is the most abundant unsaturated hydrocarbon in Titan s atmosphere. Our results indicate that the aerosols can act as activation centers to drive the photoreactivity of acetylene with the aerosols at the accretion interface at wavelengths where acetylene-ice alone does not show photoreactivity. We found that along with photochemistry, photodesorption plays an important role. We observed that about 15% of the initial acetylene is photodesorbed, with a photodesorption rate of (2.1 +/- 0.2) x 10-6 molecules.photon-1 at 355 nm. This photodesorption is wavelength-dependent, confirming that it is mediated by the UV absorption of the aerosol analogues, similar to photochemistry. We conclude that the UV-Vis properties of aerosols would determine how they evolve further in Titan s atmosphere and on the surface through photochemical alterations involving longer wavelength photons.

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arXiv2018

Organic chemistry in a CO2 rich early Earth atmosphere

The emergence of life on the Earth has required a prior organic chemistry leading to the formation of prebiotic molecules. The origin and the evolution of the organic matter on the early Earth is not yet firmly understood. Several hypothesis, possibly complementary, are considered. They can be divided in two categories: endogenous and exogenous sources. In this work we investigate the contribution of a specific endogenous source: the organic chemistry occurring in the ionosphere of the early Earth where the significant VUV contribution of the young Sun involved an efficient formation of reactive species. We address the issue whether this chemistry can lead to the formation of complex organic compounds with CO2 as only source of carbon in an early atmosphere made of N2, CO2 and H2, by mimicking experimentally this type of chemistry using a low pressure plasma reactor. By analyzing the gaseous phase composition, we strictly identified the formation of H2O, NH3, N2O and C2N2. The formation of a solid organic phase is also observed, confirming the possibility to trigger organic chemistry in the upper atmosphere of the early Earth. The identification of Nitrogen-bearing chemical functions in the solid highlights the possibility for an efficient ionospheric chemistry to provide prebiotic material on the early Earth.

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arXiv2017

Molecular Isomer Identification of Titan Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation

The chemical composition of Titan organic haze is poorly known. To address this issue, laboratory analogs named tholins are synthesized, and analyzed by methods requiring often an extraction process in a carrier solvent. These methods exclude the analysis of the insoluble tholins fraction and assume a hypothetical chemical equivalence between soluble and insoluble fractions. In this work, we present a powerful complementary analysis method recently developed on the DESIRS VUV synchrotron beamline at SOLEIL. It involves a soft pyrolysis of tholins at ~230 deg C and an electron ion coincidence analysis of the emitted volatiles compounds photoionized by the tunable synchrotron radiation. By comparison with reference photoelectron spectra (PES), the spectral information collected on the detected molecules yields their isomeric structure. The method is more readily applied to light species, while for heavier ones the number of possibilities and the lack of PES reference spectra in the literature limit its analysis. A notable pattern in the analyzed tholins is the presence of species containing adjacent doubly-bonded N atoms, which might be a signature of heterogeneous incorporation of N2 in tholins.

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arXiv2014

Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young solar system and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan s atmosphere and in the protosolar nebula, respectively. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25 permil relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among solar system objects and reservoirs. Extreme N isotope signatures in the solar system are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan s atmosphere. We also suggest that the low delta15N values of Archaean organic matter are partly the result of abiotic synthesis of organics that occurred at that time.

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