Plasma-chemical reactions in weakly decomposed CCl4

For the case of weak feed gas decomposition, where the concentration of CCl₄ exceeds those of decomposition and built-up products, the emission of CCl* is shown to originate from dissociative excitation of CCl₄. With electron concentration measured independently, the kinetics of CCl₄ decomposition has been extracted from the time dependence of the CCl* intensity. Supported by EPR determinations of radical concentrations in rapidly flowing CCl₄ and CCl₄/O₂ afterglows, the primary decomposition reaction is shown to be the electron impact dissociation into CCl₃ and Cl. Its rate constant (k ₁=4×10^–8 cm³s^–1) indicates strongly that dissociative electron attachment is the main reaction channel at least at r.f. power densities just above the threshold of a self-maintaining discharge. At extremely low mean electron energies the emission of a continuum is observed, which is tentatively ascribed to the radiative CCl₃-Cl recombination.     

Low energy electron impact on chlorofluoromethanes and CF4: Resonances,dissociative attachment and excitation

Electron transmission spectra, dissociative attachment studies and threshold electron-impact excitation spectra are presented for CFCl₃, CF₂Cl₂, CF₃Cl and CF₄. Sharp vibrational progressions, which are ascribed to a new type of resonance, have been discovered in transmission spectra below 2 eV. A survey is given of the dissociative attachment processes in the compounds studied. Some of these processes have not been described previously. New assignments are suggested for the optical spectrum of CF₃Cl. Approximate triplet energies of the chlorofluoromethanes and the chlorornethanes are given.     

Modelling of the Plasma–Sheath Boundary Region in Wall-Stabilized Arc Plasmas: Unipolar Discharge Properties

A two-dimensional model of the non-equilibrium unipolar discharge occurring in the plasma–sheath boundary region of a transferred-arc was developed. This model was used to study the current transfer to the nozzle (1 mm diameter) of a 30 A arc cutting torch operated with oxygen. The energy balance and chemistry processes in the discharge were described by using a kinetic block of 45 elementary reactions and processes with the participation of 13 species including electronically excited particles. The nonlocal transport of electrons was accounted for into the fluid model. The dependence of the ion mobility with the electric field was also considered. Basic discharge properties were described. It has been found that a large part (~ 80%) of the total electric power (1700 mW) delivered in the bulk of the sheath region is spent in heating the positive ions and further dissipated through collisions with the neutral particles. The results also showed that the electron energy loss in inelastic collisions represents only ~ 25% of the electron power and that about 63% of the power spent on gas heating is produced by the ion–molecule reaction, the electron–ion and ion–ion recombination reactions, and by the electron attachment. The rest of the power converted into heat is contributed by dissociation by electron-impact, dissociative ionization and quenching of O(¹D). Some fast gas heating channels which are expected to play a key role in the double-arcing phenomena in oxygen gas were also identified.     

Low-energy electron scattering by methane,arsine and phosphine

We present cross sections for the elastic scattering of low-energy electrons by phosphine (PH₃) and arsine (AsH₃), and for electron-impact excitation of the (1t ₂ 3sa ₁)³ T ₂ and¹ T ₂ states in methane (CH₄). These results were calculated using the Schwinger multichannel method as implemented on distributed-memory parallel computers. The PH₃ and AsH₃ cross sections show a pronounced low-energy shape resonance which may provide a pathway to dissociative attachment. The^1,3 T ₂ cross sections for CH₄ correlate fairly well with recent measurements of CH₂ production via electron-impact dissociation of methane.Contribution No. 8587     

On the Use of Global Kinetics Models for the Investigation of Energy Deposition and Chemistry in RF Argon–Oxygen Plasmas Working in the Torr Regime

A global plasma model is used to investigate the chemistry and energy deposition in 13.56 MHz radio-frequency capacitively coupled oxygen–argon discharges under conditions usually used for the deposition of tin oxide films. These models are based on the solution of a stationary electron Boltzmann equation coupled to species balance equations including the vibrational kinetics equations of O₂. The results obtained showed that vibrational non equilibrium of O₂-molecule is not significant. The dissociation degree of O₂ was found to be around a few percents and the discharge was often moderately electronegative even for small O₂ contents in the feed gas. The ionization and energy dissipation mechanisms are mainly governed by the collisional processes involving O₂ for an oxygen feed gas composition greater than 20%. Results also showed that the predicted densities of the charged species and the electronegative character of the discharge are strongly linked to the assumption made on the homogeneity of the power deposition. On the contrary, the predicted density of O-atom is not sensitive to this assumption.     

Dissociative Adsorption of H2S on Li(110) Surface Using Density Functional Theory Calculations and Car-Parrinello Molecular Dynamics Simulations

The information concerning dissociative adsorption of H₂S on Li surface is inadequate and the mechanistic insight for its complete dissociation is yet to be explored. The present investigation aims to scrutinize the dissociative adsorption of H₂S on Li(110) surface using density functional theory calculations. The climbing image nudged elastic band calculation was employed to unveil the relative energy profiles for S−H dissociation. To elucidate the components of interaction energy responsible for stabilizing the adsorbed moieties on the surface, periodic energy decomposition analysis was performed. A Car-Parrinello molecular dynamics (CPMD) simulation was performed to understand the dynamic behaviour of H₂S on Li(110). Results vividly demonstrates: (i) partially dissociated product with perpendicular S−H is comparatively stable than the parallel SH, (ii) completely dissociated moieties H/H/S are the most stable among all, (iii) dissociation of first S−H is barrierless and the second S−H dissociation is a low energy barrier reaction, (iv) complete dissociation of H₂S occurs in a stepwise manner, (v) orbital and electrostatic contributions of the interaction energy plays a vital role in stabilizing the dissociated moieties, and (vi) stepwise dissociation of H₂S was further reinforced by CPMD.     

Resonant Fragmentation of the Water Cation by Electron Impact: a Wave-Packet Study

We have investigated the dissociation of a resonant state that can be formed in low energy electron scattering from H₂O⁺. We have chosen the second triplet resonance above the state of H₂O⁺ whose autoionization mainly produces H₂O⁺ ( ). We have considered both dissociation of the resonant state itself, dissociative recombination (DR), or the dissociation of the H₂O⁺ cation after autodetachment, dissociative excitation (DE). The time-evolution of a wave packet on the potential energy surfaces of the resonance and cationic states shows, for the initial conditions studied, that the probability for DR is about 38 % while the probability for DE is negligible.     

Bounday trajectories in collision-induced dissociation

The boundary trajectories separating non-reactive, reactive, and dissociative bands of trajectories in atom—diatom collision-induced dissociation are defined. Trajectory calculations are reported for the collinear H + H₂ reaction which demonstrate how the boundary trajectories can be used to obtained information on the non-reactive, reactive, and dissociative regions of the reagents phase space.     

A decrease in the ignition temperature of molecular systems during nonequilibrium vibrational excitation of reacting molecules

The nonequilibrium vibrational excitation of reacting molecules can result in a substantial (up to 100%) decrease in the temperature threshold of self-ignition in the H₂ + air system. In this case, dissociation reactions are responsible for the formation of active species that initiate chain combustion. An increase in temperature during the induction period caused by the recombination of oxygen and hydrogen atoms and OH radicals formed plays an important role in the intensification of chain reactions and self-ignition of the mixture at low temperatures (∼300-400 K)     

Dissociative chemisorption and energy transfer for methane on Ir(111)

A 3-parameter local hot spot model of gas-surface reactivity is employed to analyze and predict dissociative sticking coefficients for CH(4) incident on Ir(111) under varied nonequilibrium and equilibrium conditions. One Ir surface oscillator and the molecular vibrations, rotations, and translational energy directed along the surface normal are treated as active degrees of freedom in the 14 dimensional microcanonical kinetics. The threshold energy for CH(4) dissociative chemisorption on Ir(111) derived from modeling molecular beam experiments is E(0) = 39 kJ/mol. Over more than 4 orders of magnitude of variation in sticking, the average relative discrepancy between the beam and theoretically derived sticking coefficients is 88%. The experimentally observed enhancement in dissociative sticking as beam translational energies decrease below approximately 10 kJ/mol is consistent with a parallel dynamical trapping/energy transfer channel that likely fails to completely thermalize the molecules to the surface temperature. This trapping-mediated sticking, indicative of specific energy transfer pathways from the surface under nonequilibrium conditions, should be a minor contributor to the overall dissociative sticking at thermal equilibrium. Surprisingly, the CH(4) dissociative sticking coefficient predicted for Ir(111) surfaces at thermal equilibrium, based on the molecular beam experiments, is roughly 4 orders of magnitude higher than recent measurements on supported nanoscale Ir catalysts at 1 bar pressure, which suggests that substantial improvements in catalyst turnover rates may be possible.     

Study of Mechanism for Hexane Decomposition with Gliding Arc Gas Discharge

The mechanism of hexane decomposition under gliding arc gas discharge conditions is studied from both qualitative and quantitative analyses of its products for various hexane initial concentrations and different background atmospheres : nitrogen, argon, air (O₂ 21% N₂ 79% vol.) and N₂–O₂ mixtures. The decomposition rate, which decreases with increasing hexane initial concentration, can reach 94% when the carrier gas is air. Due to the electron energy consumed by the dissociation of nitrogen, the decomposition rate of hexane in nitrogen is lower than in argon. The radical channel plays a predominant role in the hexane decomposition process. With increasing oxygen concentration in the carrier gas, the hexane decomposition rate increases and promotes the conversion of CO– CO₂, but it also leads to the formation of NO₂.     

The role of dissociative attachment from Rydberg states in enhancing H concentration in moderate- and low-pressure H2 plasma sources

A numerical code, recently developed for describing the kinetics of H₂ microwave discharges obtained in diamond deposition plasma reactors, was used to estimate the importance of dissociative attachment from H₂ Rydberg states in enhancing the production of H⁻ in this kind of discharge. It was also used to investigate H⁻ production in multicusp low-pressure magnetic plasmas. Results show that the dissociative attachment from Rydberg states can be as important as the mechanism involving vibrationally excited molecules in both types of plasmas.     

ZnO Nanocluster as a Potential Catalyst for Dissociation of H2S Molecule

Adsorption of hydrogen sulfide (H₂S) on the external and internal surface of Zn₁₂O₁₂ nanocluster was studied by using density functional calculations. The results indicate that the H₂S molecule is physically adsorbed or chemically dissociated by the nanocluster. It was found that the H₂S molecule can dissociate into –H and–SH fragments, suggesting that the nanocluster might be a potential catalyst for dissociation of the H₂S molecule. Also, dissociation of H₂S to S species in internal surface of the Zn₁₂O₁₂ nanocluster is energetically impossible. The HOMO–LUMO energy gap of H₂S dissociation configuration is changed about 27.68 %, indicating that the electronic properties of the nanocluster by dissociation process have strongly changed.     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.     

Reactions in Tirapazamine Induced by the Attachment of Low‐Energy Electrons: Dissociation Versus Roaming of OH

Tirapazamine (TPZ) has been tested in clinical trials on radio‐chemotherapy due to its potential highly selective toxicity towards hypoxic tumor cells. It was suggested that either the hydroxyl radical or benzotriazinyl radical may form as bioactive radical after the initial reduction of TPZ in solution. In the present work, we studied low‐energy electron attachment to TPZ in the gas phase and investigated the decomposition of the formed TPZ^? anion by mass spectrometry. We observed the formation of the (TPZ–OH)^? anion accompanied by the dissociation of the hydroxyl radical as by far the most abundant reaction pathway upon attachment of a low‐energy electron. Quantum chemical calculations suggest that NH₂ pyramidalization is the key reaction coordinate for the reaction dynamics upon electron attachment. We propose an OH roaming mechanism for other reaction channels observed, in competition with the OH dissociation.     

A critical evaluation of low-energy electron impact cross sections for plasma processing modeling. I: Cl2, F2, and HCl

The available information on low-energy electron impact cross sections for Cl₂, F₂, and HCAl is reviewed and critically evaluated. Of interest are the cross sections for momentum transfer; rotational, vibrational, and electronic excitation (with possible dissociation); and attachment and ionization. The bulk of the data available for these molecules are on dissociative attachment, as that is the property, that has been of greatest interest in applications and is relatively easy to measure. Much of the process of critical evaluation is performed by computing electron transport, or swarm, coefficients using the published cross sections and comparing with published measurements. What little is known about electronic excitation or dissociation processes is theoretical or even guessed at using analogies to processes in other molecules. Recommended cross sections are identified where feasible.     

Role of excited core Rydberg states in dissociative recombination

Intermediate states formed during the dissociative recombination of molecular ions with electrons can play significant roles in determining the magnitude of the total rate coefficient. These resonances are Rydberg states of two types, that is, they can have the ground or excited states of the ion as a core. Those with the excited cores have a fundamentally different excitation mechanism than those with the ground state core. The importance of excited core states in dissociative recombination has received only limited attention in the literature. Theoretical calculations on the dissociative recombination of N2+ are reported which compare the two types of resonances. Potential curves, electronic widths, cross sections, and rate coefficients are calculated for dissociative recombination along the 2(1)Sigma(g)+ state, one of several routes for the dissociative recombination of N2+. The ground core resonances, in this example, are relatively unimportant compared to those with the excited core. Inclusion of the excited core resonances increases the rate coefficient by about a factor of 4 at room temperature, but the increase is not enough to establish 2(1)Sigma(g)+ as the dominant dissociative route.     

Quantum mechanics investigation on initial decomposition of ammonia borane in glyme

The chemical kinetics of ammonia borane (AB) in glyme solution is studied using quantum mechanics (QM) based calculations along with experimental results available in the literature. The primary objective of this study is to propose a detailed reaction mechanism that explains the formation of species observed during AB decomposition for temperatures ranging from 323 to 368 K. The quantum mechanics investigation uses transition state theory to identify the relevant reaction pathways. Intrinsic reaction coordinate calculations use the identified transition‐state structure to link the reactants to the products. These calculations were performed using the Gaussian 09 program package, including the solvation model based on density (SMD) with acetonitrile as the solvent. Thermodynamic properties of species at equilibrium or at transition states were computed using the G4(MP2) compound method. Sensitivity analysis was performed using a species conservation model to identify reactions and species that play a critical role. This study confirms the previous experimental observation regarding the initiation of decomposition of AB in glyme. It also elucidates the role of DADB, ammonium borohydride salt ([BH₄]⁻[NH₄]⁺) and BH₂NH₂ in hydrogen release and intermediates formed during initial phase of AB decomposition. This work shows how QM calculations along with experimental results can contribute to our understanding of the complex chemical kinetics involved during AB dehydrogenation.     

The efficacy of heating low-pressure H2 in a microwave discharge

The relative ease with which a low-pressure hydrogen stream may be heated in an electrical discharge suggests that such a system be considered in current efforts to develop thrusters for spacecraft orbit raising purposes. In this work a detailed model of a microwave discharge in flowing, low-pressure hydrogen is used to interpret and clarify experimental measurements of atom concentration, electron energy, and electron density. The radially averaged, constant-pressure model accurately reproduces the experimental data and also calculated the rates of a number of gas-heating and wall-heating processes as well as rates of energy deposition into coolant and working fluid streams. The calculated gas-heating rates indicate that the gas heating is due primarily to the thermalization of the energetic atoms produced by dissociation of H₂ via excitation of theb ³∑ _u ⁺ state. The calculations also indicate that the energy flux to the quartz tube is significantly influenced by Lyman and Werner band radiation and by heterogeneous atomic recombination processes and, to a much lesser degree, by electron-ion recombination processes. The fraction of power input which is ultimately transferred to the gas stream is a decreasing function of the power input and varies from 0.24 to 0.12.