Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 micrometer suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation. In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogues, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogues. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a {\lambda}=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine

Characterization of a DC glow discharge in N2-H2 with electrical measurements and neutral and ion mass spectrometry

The addition of small amounts of H2 were investigated in a DC glow discharge in N2, at low pressure (~1 mbar) and low power (0.05 to 0.2 W.cm-3). We quantified the electric field, the electron density, the ammonia production and the formation of positive ions for amounts of H2 varying between 0 and 5%, pressure values between 0.5 and 4 mbar, and currents between 10 and 40 mA. The addition of less than 1% H2 has a strong effect on the N2 plasma discharges. Hydrogen quenches the (higher) vibrational levels of N2 and some of its highly energetic metastable states. This leads to the increase of the discharge electric field and consequently of the average electron energy. As a result, higher quantities of radical and excited species are suspected to be produced. The addition of hydrogen also leads to the formation of new species. In particular, ammonia and hydrogen-bearing ions have been observed: N2H+ and NH4+ being the major ones, and also H3+, NH+, NH2+, NH3+, N3H+ and N3H3+. The comparison to a radiofrequency capacitively coupled plasma (RF CCP) discharge in similar experimental conditions shows that both discharges led to similar observations. The study of N2-H2 discharges in the laboratory in the adequate ionization conditions then gives some insights on which plasma species made of nitrogen and hydrogen could be present in the ionosphere of Titan. Here, we identified some protonated ions, which are reactive species that could participate to the erosion of organic aerosols on Titan.Comment: Paper accepted in Plasma Sources Science and Technology in March 2023. The current version on arXiv is the submitted versio

Experiments and modelling in N2-H2 capacitively coupled radio-frequency discharges at low pressure

This work uses experiments and simulations to analyze the modifications induced in pure N2 capacitively coupled radio-frequency discharges, running at low pressure (0.6–1.2 mbar) and low power (5–20 W), by the addition of small amounts of H2 (up to 5%). Simulations use a hybrid code coupling a two-dimensional time-dependent fluid module, describing the dynamics of the charged particles, to a zero-dimensional kinetic module, describing the production and destruction of nitrogen and hydrogen neutral species. The discussion is particularly focused on the results obtained for the electron density and the radiative transition intensities with nitrogen species. Model predictions are in qualitative agreement with measurements, for the evolution of these quantities with changes in both the gas pressure and the hydrogen percentage in the gas mixture.Fundação para a Ciência e a Tecnologia (FCT

Gaseous chemistry for a Titan's atmospheric plasma experimental simulation

We present the first study of gaseous composition monitoring for the PAMPRE experiment, which simulates Titan's atmospheric chemistry by radio-frequency N 2-CH 4 plasma. Methane consumption is quantified for various N 2-CH 4 gas mixtures. Moreover in situ mass spectrometry (MS) and ex-situ gas chromatography coupled with mass spectrometry (GC-MS) analyses reveal a large dominance of nitrile species in the gas phase chemistry

N2-H2 capacitively coupled radio-frequency discharges at low pressure: II. Modeling results: The relevance of plasma-surface interaction

In this work, we present the results of simulations carried out for N2-H2 capacitively coupled radio-frequency discharges, running at low pressure (0.3-0.9 mbar), low power (5-20 W), and for amounts of H2 up to 5%. Simulations are performed using a hybrid code that couples a two-dimensional time-dependent fluid module, describing the dynamics of the charged particles in the discharge, to a zero-dimensional kinetic module, that solves the Boltzmann equation and describes the production and destruction of neutral species. The model accounts for the production of several vibrationally and electronic excited states, and contains a detailed surface chemistry that includes recombination processes and the production of NH x molecules. The results obtained highlight the relevance of the interactions between plasma and surface, given the role of the secondary electron emission in the electrical parameters of the discharge and the critical importance of the surface production of ammonia to the neutral and ionic chemistry of the discharge.The Portuguese Foundation sponsored this research for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2019

Modelling of a CCP-RF discharge used for the simulation of Titan’s chemistry

This paper reports the modelling of CCP-RF discharges (13.56 MHz) in pure nitrogen, produced within a cylindrical parallel-plate reactor, similar to a GEC reference cell surrounded by a lateral grounded grid, at 0.1-2 mbar pressures and 10-50 W coupled powers. This study is a first step in simulating Titan’s chemistry at laboratory scale, using the PAMPRE experiment. Modelling results are compared with experimental measurements of the average electrondensity, and the self-bias potential at the polarized electrode

Capacitively coupled radio-frequency N2 discharges at low pressures

Capacitively coupled radio-frequency discharges (ccrf) in nitrogen mixtures are frequently used for the processing, modification and functionalization of different kinds of materials. Although nitrogen plasmas have been studied for many years, and despite their growing interest in applications, there is only partial knowledge about ccrf nitrogen plasmas. This paper uses experiments and modelling to study ccrf discharges in pure nitrogen, at 13.56 MHz frequency, 0.1–1 mbar pressures and 2–30 W coupled powers [1]. Experiments performed on two similar (not twin) setups, existing in the LATMOS and the GREMI laboratories, include electrical and optical emission spectroscopy (OES) measurements. Electrical measurements give the rf-applied and the direct-current-self-bias voltages, the effective power coupled to the plasma and the average electron density. OES diagnostics measure the intensities of radiative transitions with the nitrogen second-positive and first-negative systems, and with the 811.5 nm atomic line of argon (present as an actinometer). In the particular case of non-equilibrium ccrf discharges in nitrogen, a self-consistent modeling strategy must account for the interplay between the transport of particles, in the presence of density gradients and the rf field, and their production/destruction due to kinetic mechanisms involving both electrons and heavy species. Simulations use a hybrid code that couples a two-dimensional timedependent fluid module [2], describing the dynamics of the charged particles (electrons and positive ions N2 + and N4 +), and a zero-dimensional kinetic module, describing the production and destruction of nitrogen (atomic and molecular) neutral species [3]. The coupling between these modules adopts the local mean energy approximation to define space–time-dependent electron parameters for the fluid module and to work out space–time-averaged rates for the kinetic module. The model gives general good predictions for the self-bias voltage and for the intensities of radiative transitions (both average and spatially resolved), underestimating the electron density by a factor of 3–4.Fundação para a Ciência e a Tecnologia (FCT

Use of the linear absorption coefficient for absolute comparison of plasma films in the mid-IR range

In this work, we present the mid-infrared analysis of analogues of Titan's aerosols produced in a radio frequency capacitively coupled plasma (RF-CCP). The influence of the gas mixture on aerosols spectra is also studied through the analysis of the carbonaceous bands of the spectra, and its Gaussian deconvolution.Представлен анализ в среднем инфракрасном диапазоне аналогов титановых аэрозолей, которые производятся в радиочастотных источниках плазмы с емкостной связью (РЧ-ЕСС). Также изучено влияние газовой смеси на спектры аэрозолей с помощью анализа углеродсодержащих полос спектра и ее гауссовой деконволюции (обратная свертка).Представлено аналіз у середньому інфрачервоному діапазоні аналогів титанових аерозолів, які проводяться в радіочастотних джерелах плазми з ємнісним зв'язком (РЧ-ЕСС). Також вивчено вплив газової суміші на спектри аерозолів за допомогою аналізу вуглецевмісних смуг спектра і її гауссової деконволюції (зворотня згортка)

Use of the linear absorption coefficient for absolute comparison of plasma films in the mid-IR range

In this work, we present the mid-infrared analysis of analogues of Titan's aerosols produced in a radio frequency capacitively coupled plasma (RF-CCP). The influence of the gas mixture on aerosols spectra is also studied through the analysis of the carbonaceous bands of the spectra, and its Gaussian deconvolution.Представлен анализ в среднем инфракрасном диапазоне аналогов титановых аэрозолей, которые производятся в радиочастотных источниках плазмы с емкостной связью (РЧ-ЕСС). Также изучено влияние газовой смеси на спектры аэрозолей с помощью анализа углеродсодержащих полос спектра и ее гауссовой деконволюции (обратная свертка).Представлено аналіз у середньому інфрачервоному діапазоні аналогів титанових аерозолів, які проводяться в радіочастотних джерелах плазми з ємнісним зв'язком (РЧ-ЕСС). Також вивчено вплив газової суміші на спектри аерозолів за допомогою аналізу вуглецевмісних смуг спектра і її гауссової деконволюції (зворотня згортка)

N2-H2 capacitively coupled radio-frequency discharges at low pressure. Part I. Experimental results: Effect of the H2 amount on electrons, positive ions and ammonia formation

The mixing of N2 with H2 leads to very different plasmas from pure N2 and H2 plasma discharges. Numerous issues are therefore raised involving the processes leading to ammonia (NH3) formation. The aim of this work is to better characterize capacitively-coupled radiofrequency plasma discharges in N2 with few percents of H2 (up to 5%), at low pressure (0.3-1 mbar) and low coupled power (3-13 W). Both experimental measurements and numerical simulations are performed. For clarity, we separated the results in two complementary parts. The actual one (first part), presents the details on the experimental measurements, while the second focuses on the simulation, a hybrid model combining a 2D fluid module and a 0D kinetic module. Electron density is measured by a resonant cavity method. It varies from 0.4 to 5 109 cm-3, corresponding to ionization degrees from 2 10-8 to 4 10-7. Ammonia density is quantified by combining IR absorption and mass spectrometry. It increases linearly with the amount of H2 (up to 3 1013 cm-3 at 5% H2). On the contrary, it is constant with pressure, which suggests the dominance of surface processes on the formation of ammonia. Positive ions are measured by mass spectrometry. Nitrogen-bearing ions are hydrogenated by the injection of H2, N2H+ being the major ion as soon as the amount of H2 is >1%. The increase of pressure leads to an increase of secondary ions formed by ion/radical-neutral collisions (ex: N2H+, NH4 +, H3 +), while an increase of the coupled power favours ions formed by direct ionization (ex: N2 +, NH3 +, H2 +).N. Carrasco acknowledges the financial support of the European Research Council (ERC Starting Grant PRIMCHEM, Grant agreement no. 636829). A. Chatain acknowledges ENS Paris-Saclay Doctoral Program. A. Chatain is grateful to Gilles Cartry and Thomas Gautier for fruitful discussions on the MS calibration. L.L. Alves acknowledges the financial support of the Portuguese Foundation for Science and Technology (FCT) through the project UID/FIS/50010/2019. L. Marques and M. J. Redondo acknowledge the financial support of the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2019