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The role of anisotropic scattering in rotational collisions of electrons with CO molecules is investigated numerically with Monte Carlo (MC) simulations and with calculations using the Lisbon KInetics two-term Boltzmann solver (LoKI-B). The study adopts integral cross sections taken from the IST-Lisbon database of LXCat or extracted from Biagi's code Magboltz v11.10. Different angular scattering models for rotational collisions are implemented and compared in MC simulations, and a novel anisotropic scattering model is derived from the dipole-Born differential cross sections, to describe the strongly forward-peaked nature of rotational collisions. This model is also implemented in LoKI-B, to describe the anisotropic inelastic/superelastic scattering in dipole rotational collisions, using coherent expressions for the corresponding integral and momentum transfer cross sections. The comparison between MC and LoKI-B results shows that the calculation of swarm parameters is more influenced by the choice of the angular scattering model than the adoption of the two-term approximation, yielding deviations up to 50% in the reduced mobility for different angular distributions. The consequences in the swarm derivation of cross sections are also discussed. Finally, it is shown that inclusion of electric-quadrupole interactions, usually neglected in electron swarm studies, can improve the agreement between numerical results and measurements. [ABSTRACT FROM AUTHOR]

This work analyzes the temporal evolution of the electron kinetics in dry-air plasmas (80% N2: 20% O2), excited by electric-field pulses with typical rise-times of 10−9 and 10−6 s, applied to a stationary neutral gaseous background at pressures of 105, 133 Pa and temperature of 300 K. The study is based on the solution of the electron Boltzmann equation (EBE), adopting either (i) a time-dependent formulation that considers an intrinsic time evolution for the electron energy distribution function (EEDF), assuming the classical two-term expansion and a space-independent exponential temporal growth of the electron density; or (ii) a quasi-stationary approach, where the time-independent form of the EBE is solved for different values of the reduced electric-field over the duration of the pulse. The EBE was solved using the LisbOn KInetics Boltzmann solver (LoKI-B), whose original capabilities were extended to accept time-dependent non-oscillatory electric fields as input data. The role of electron–electron collisions, under specific conditions, is also reported and discussed. The simulations show that the quasi-stationary approach gives solutions similar to the time-dependent formulation for rise-times longer than the characteristic evolution time of the EEDF, i.e. 20 ns at 105 Pa and 20 μs at 133 Pa, meaning that a quasi-stationary description is possible in a high-collisionality situation and long rise-times (e.g. microsecond pulses at atmospheric pressure), failing for faster rise-times (e.g. nanosecond pulses for both pressures considered here). [ABSTRACT FROM AUTHOR]

It has been recently advocated that Mars has excellent conditions for oxygen and fuel production directly from atmospheric CO2 using non-equilibrium plasmas. The Martian conditions would be favorable for vibrational excitation and/or enhanced dissociation by electron impact, two important pathways for CO2 plasma dissociation. Herein we confirm these theoretical predictions by measuring, for the first time, the vibrational temperatures of CO2 and the CO and CO2 concentrations in realistic Martian conditions. In situ Fourier transform infrared spectroscopy measurements are performed in experiments conducted in DC glow discharges operating at pressures p = 1–5 Torr, discharge currents I = 10–50 mA, initial gas temperatures of 220 K and 300 K, both in pure CO2 and in the synthetic Martian atmosphere 96% CO2–2% Ar–2% N2. To analyze and interpret the experimental results, we develop a detailed self-consistent kinetic model for pure CO2 plasmas, describing the coupled electron and heavy-particle kinetics. The simulation results are in very good agreement with the experimental data. It is shown that the low-temperature conditions may enhance the degree of vibrational non-equilibrium and that the Martian atmospheric composition has a positive effect on CO2 decomposition. Accordingly, the present investigation confirms the potential of plasma technologies for in situ resource utilization on Mars. [ABSTRACT FROM AUTHOR]

The use of plasmas for CO2 utilization has been under investigation in recent years following a wave of environmental awareness. In this work, previously published experimental results on vibrationally cold CO2 plasmas are modelled to define a reaction mechanism, i.e. a set of reactions and rate coefficients validated against benchmark experiments. The model couples self-consistently the electron and heavy particle kinetics. In turn, the simulated results are validated against measurements taken in CO2 DC glow discharges in a relatively large range of experimental conditions: at pressures from 0.4 to 5 Torr, reduced electric fields ranging from 50 to 100 Td and gas flowing from 2 to 8 sccm. The model predicts the measured values of product formation (CO and O) as well as discharge power and electric field. After validation, a thorough analysis of the model's results is presented, including: electron properties, species densities, power distribution into different excitation channels and main creation and destruction mechanisms of the main species. It is shown that, although vibrational populations are low, they have a significant effect on the electron properties and thus on the electric field and conversion. Moreover, the shape of the EEDF is significantly dependent on the dissociation degree. The role of electronically excited states on CO2 dissociation is also analyzed, showing that the first electronic excited state of CO can have a beneficial or detrimental effect in further producing CO and O in the discharge. [ABSTRACT FROM AUTHOR]

Plasma has been studied for several years to convert CO2 into value-added products. If CO2 could be converted in the presence of H2O as a cheap H-source for making syngas and oxygenates, it would mimic natural photosynthesis. However, CO2/H2O plasmas have not yet been extensively studied, not by experiments, and certainly not computationally. Therefore, we present here a kinetic modelling study to obtain a greater understanding of the vibrational kinetics of a CO2/H2O microwave plasma. For this purpose, we first created an electron impact cross section set for H2O, using a swarm-derived method. We added the new cross section set and CO2/H2O-related chemistry to a pure CO2 model. While it was expected that H2O addition mainly causes quenching of the CO2 asymmetric mode vibrational levels due to the additional CO2/H2O vibrational-translational relaxation, our model shows that the modifications in the vibrational kinetics are mainly induced by the strong electron dissociative attachment to H2O molecules, causing a reduction in electron density, and the corresponding changes in the input of energy into the CO2 vibrational levels by electron impact processes. [ABSTRACT FROM AUTHOR]

Several CO2 electron impact dissociation cross sections are available in the literature, different in magnitude and threshold, hindering the understanding of CO2 dissociation mechanisms under gas discharges. This work reports the experimental validation of the electron impact CO2 dissociation cross section using two complementary methods: through the comparison of the measured rate coefficients with those derived from cross sections available in literature; and through the comparison of the experimental time evolution of the dissociation fraction with the simulations of a 0D model. A careful experimental approach was designed to avoid any influence from other dissociation mechanisms or chemical reactions. The experimental results match remarkably well the theoretical predictions from Polak and Slovetsky and establish the validity of the dissociation rate coefficients derived from their cross section. This validation supports the use of Polak and Slovetsky's cross section in any theoretical or modelling approach involving CO2 molecules under electrical discharges. [ABSTRACT FROM AUTHOR]

Oxygen atom densities were measured in situ in a CO2 glow discharge, at pressures between 0.2 and 5 Torr (26.7–666.6 Pa). Two measurement techniques were compared, namely optical emission actinometry (using Ar as the actinometer) and high-resolution two-photon absorption laser induced fluorescence normalised to Xe, and were found to give consistent results. The variation of the atomic oxygen density with gas pressure shows two different regimes with a transition around 1 Torr. Measurements of the O atom loss frequency under plasma exposure showed that this behaviour is caused by a change in the O atom loss mechanisms, which are dominated by surface processes in our experimental conditions. The corresponding recombination probabilities on Pyrex γO are found to vary with the gas temperature near the wall for a constant surface temperature, similarly to what has recently been obtained in pure O2. However, the measured values are more than two times lower than γO obtained in a O2 plasma in similar conditions. The O atom densities are also compared to the dissociation fraction of CO2 determined by infra-red absorption. The obtained CO and O densities show different behaviour as a function of the energy input. The simultaneous measurement of gas temperature, electric field, O, CO and CO2 densities and O atoms loss frequency in the same conditions provides an ideal set of constraints for validating CO2 plasma kinetic models. [ABSTRACT FROM AUTHOR]

The recombination of O (3P) atoms on the surface of a Pyrex tube containing a DC glow discharge in pure O2 was studied over a wide range of pressure (0.2–10 Torr) and discharge current (10–40 mA) for two fixed surface temperatures (+50 °C and +5 °C). The recombination probability, γ, was deduced from the observed atom loss rate (dominated by surface recombination) determined by time-resolved optical emission actinometry in partially-modulated (amplitude ∼15%–17%) discharges. The value of γ increased with discharge current at all pressures studied. As a function of pressure it passes through a minimum at ∼0.75 Torr. At pressures above this minimum γ is well-correlated with the gas temperature, Tg, (determined from the rotational structure of the O2 (b1Σg+, v = 0) → O2(X3Σg−, v = 0) emission spectrum) which increases with pressure and current. The temperature of the atoms incident at the surface was deduced from a model, calibrated by measurements of the spatially-averaged gas temperature and validated by radial temperature profile measurements. The value of γ follows an Arrhenius law depending on the incident atom temperature, with an activation energy in the range 0.13–0.16 eV. At the higher surface temperature the activation energy is the same, but the pre-exponential factor is smaller. Under conditions where the O flux to the surface is low γ falls below this Arrhenius law. These results are well explained by an Eley–Rideal (ER) mechanism with incident O atoms recombining with both chemisorbed and more weakly bonded physisorbed atoms on the surface, with the kinetic energy of the incident atoms providing the energy to overcome the activation energy barrier. A phenomenological ER model is proposed that explains both the decrease in recombination probability with surface temperature as well as the deviations from the Arrhenius law when the O flux is low. At pressures below 0.75 Torr γ increases significantly, and also increases strongly with the discharge current. We attribute this effect to incident ions and fast neutrals arriving with sufficient energy to clean or chemically modify the surface, generating new adsorption sites. Discharge modeling confirms that at pressures below ∼0.3 Torr a noticeable fraction of the ions arriving at the surface have adequate kinetic energy to break surface chemical bonds (>3–5 eV). [ABSTRACT FROM AUTHOR]

A self-consistent model is developed to study the temporal variation of the gas temperature in millisecond single dc pulsed discharges and their afterglows in air-like mixtures (N2–20%O2) at low pressures. The model is based on the solutions to the time-dependent gas thermal balance equation, under the assumption of a parabolic gas temperature profile across the discharge tube, coupled to the electron, vibrational and chemical kinetics. Modelling results provide a satisfactory explanation for recently published time-resolved experimental data for the gas temperature in a 5 ms pulsed air plasma with a current of 150 mA and the corresponding afterglow at a pressure of 133 Pa (1 Torr). It is shown that the main heating mechanisms during the first millisecond of the pulse come predominantly from O2 dissociation by electron impact through the pre-dissociative excited state and the quenching of nitrogen electronically excited states , B3∏g, , a1∏g, w1Δu) by O2, agreeing with other studies on fast gas heating in air plasmas. As the pulse duration increases, other gas heating sources become important, namely V–T N2–O energy exchanges, recombination of oxygen atoms at the wall, N2(A) quenching by O(3P) and reaction N(4S) + NO(X) → N2(X, v ∼ 3) + O, contributing altogether to an additional smooth increase in the gas temperature until the end of the pulse. In the first instants of the early afterglow, the gas temperature decreases very rapidly as a consequence of the minor role played by electronic collisions and due to a fast decay of N2 electronic states. For afterglow times up to 10 ms, the gas temperature continues to decrease, following the time-dependent kinetics of [N2(X, v)], [N(4S)], [O(3P)] and [NO(X)]. Sensitivity of the model to different input parameters such as thermal accommodation coefficient and probabilities for atomic recombination at the wall are reported. [ABSTRACT FROM AUTHOR]

Several CO2 electron impact dissociation cross sections are available in the literature, different in magnitude and threshold, hindering the understanding of CO2 dissociation mechanisms under gas discharges. This work reports the experimental validation of the electron impact CO2 dissociation cross section using two complementary methods: through the comparison of the measured rate coefficients with those derived from cross sections available in literature; and through the comparison of the experimental time evolution of the dissociation fraction with the simulations of a 0D model. A careful experimental approach was designed to avoid any influence from other dissociation mechanisms or chemical reactions. The experimental results match remarkably well the theoretical predictions from Polak and Slovetsky and establish the validity of the dissociation rate coefficients derived from their cross section. This validation supports the use of Polak and Slovetsky's cross section in any theoretical or modelling approach involving CO2 molecules under electrical discharges. [ABSTRACT FROM AUTHOR]