This work addresses plasma chemistry in the core of a vortex-stabilized microwave discharge for CO ₂ conversion numerically, focusing on the pressure-dependent contraction dynamics of this plasma. A zero-dimensional model is presented for experimental conditions in a pressure range between 60 and 300 mbar and a temperature range between 3000 and 6500 K. Monte Carlo flux (MCF) simulations, which describe electron kinetics, are self-consistently coupled to the plasma chemistry model. The simulation results show that an increase in pressure is accompanied by a transition in neutral composition in the plasma core: from a significant amount of CO ₂ and O ₂ at low pressures to a O/CO/C mixture at high pressures, the composition being determined mostly by thermal equilibrium and by transport processes. The change of temperature and composition with pressure lead to higher ionisation coefficient and more atomic ion composition in the plasma core. These changes result in an increase in ionisation degree in the plasma core from 10 ⁻⁵ to 10 ⁻⁴ . These factors are shown to be fundamental to drive contraction in the CO ₂ microwave discharge.

This work investigates kinetics and transport of CO₂ microwave plasmas through simulation results from a 1D radial fluid model and experiments. Simulation results are validated against spatially resolved measurements of neutral species mole fractions, gas temperature, electron number density and temperature obtained by means of Thomson and Raman scattering diagnostics, yielding good agreement. As such, the model is used to complement experiments and assess the main chemical reactions, mass and energy transport in diffuse and contracted plasma regimes. From model results, it is found that, as pressure is raised, the inhomogeneous gas heating induces significant gradients in neutral and charged species mole fractions profiles. Moreover, the transition from diffuse to contracted plasma is accompanied by a change in the dominant charged species, which favours electron–ion recombination over dissociative attachment. Associative ionization rates increase in the plasma core from diffuse to contracted regime. These processes contribute to the increase in the peak electron number density with pressure, that determines radial plasma contraction.

This work proposes a complete and consistent set of cross sections (CSs) for electron collisions with water molecules to be published in the IST-Lisbon database on LXCat. The set is validated from the comparison between experimental and computed electron swarm parameters. The former are collected from literature while the latter are calculated using a space-homogeneous two-term Boltzmann solver, assuming isotropic scattering in inelastic collisions. Rotational CSs, based on the Born approximation, are optimised by means of the electron swarm analysis technique. Superelastic rotational and vibrational collisions are accounted for in the calculations and found to be particularly important for low-energy electrons interacting with water molecules. The set can be used with codes assuming space-homogeneous conditions, in particular common two-term Boltzmann solvers, ensuring a good agreement with experiments. Therefore, it constitutes an important tool for fast calculations and modelling of complex plasma chemistries.

A method is proposed to spatially resolve discharge parameters from experimental measurements of emission intensity and 1D numerical simulations including an O atom collisional-radiative model. The method can be used for different plasmas and conditions. Here, contracted microwave discharges for CO ₂ conversion are studied at intermediate to high pressures (100–300 mbar). Radial profiles of electron density ( n _e ) are used as input in the model and corrected to successfully simulate the measured Gaussian profiles of emission intensity of the 777 nm transition ( I ₇₇₇ ). As a result, radially-resolved parameters inaccessible in experiments, such as n _e , power density ( P _abs ), electron temperature ( T _e ), electric field and reaction rates, are numerically-obtained for several conditions. n _e and P _abs approximately follow Gaussian profiles that are broader than that of I ₇₇₇ . For pressures below 150 mbar, the difference in full width at half maximum is typically a factor 1.6. This consists in a phenomenon of optical contraction, which is due to concave profiles of O molar fraction and T _e . The implications of the simulated profiles on the study of plasmas for CO ₂ conversion are discussed and it is shown that these profiles allow to explain high reactor performances at low pressures.

Electron velocity distribution functions (EVDFs) in CO ₂ obtained by means of the Monte Carlo flux (MCF) method are compared with results from two-term and multi-term Boltzmann solvers. The MCF method provides detailed calculations of the EVDF through a highly efficient variance reduction technique. Benchmark calculations of Legendre polynomial coefficients of the EVDF expansion are reported for a wide range of reduced electric fields ( E / N ), showing excellent agreement with multi-term solutions. Rate coefficients of inelastic processes calculated from two-term Boltzmann solvers differ significantly, up to 70%, from MCF and multi-term solutions, due to the anisotropy of the EVDF. An extension of the method to consider the thermal distribution of the background gas is also presented. This extension, together with an accurate description of the population of rotationally and vibrationally excited states, provides excellent agreement with measured transport coefficients at low E / N . A good agreement is obtained at moderate E / N between experimental values of dissociation rate coefficients and MCF calculations after careful consideration and analysis of several cross sections data sets.

We review the recent progress in the modeling of plasmas or ionized gases, with compositions compatible with that of primordial atmospheres. The plasma kinetics involves elementary processes by which free electrons ultimately activate weakly reactive molecules, such as carbon dioxide or methane, thereby potentially starting prebiotic reaction chains. These processes include electron–molecule reactions and energy exchanges between molecules. They are basic processes, for example, in the famous Miller-Urey experiment, and become relevant in any prebiotic scenario where the primordial atmosphere is significantly ionized by electrical activity, photoionization or meteor phenomena. The kinetics of plasma displays remarkable complexity due to the non-equilibrium features of the energy distributions involved. In particular, we argue that two concepts developed by the plasma modeling community, the electron velocity distribution function and the vibrational distribution function, may unlock much new information and provide insight into prebiotic processes initiated by electron–molecule collisions.