Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

Monte Carlo simulations of electron dynamics in N2/CO2 mixtures

Motivated by experimental investigations of electrical discharges in N₂/CO₂/H₂O, Monte Carlo (MC) electron dynamics simulations in atmospheric N₂/CO₂ mixtures were performed. The goal was to obtain electron energy distribution functions (EEDFs), mean free path, drift velocity, collision frequency and mean energy of electrons, rate coefficients of electron-impact reactions, ionisation and attachment coefficients, as functions of the reduced electric field strength (E/N) and of the concentration of individual gas components. The results obtained by MC simulations were fitted with polynomials of up to the 3rd order with reasonable accuracy for E/N above 80 Td. The studied parameters below 80 Td were strongly non-linear as functions of E/N. This is mostly due to the influence of elastic collisions of electrons with CO₂ molecules prevailing in CO₂-dominant mixtures for E/N < 40 Td, and vibrational excitation collisions of N₂ species prevailing in N₂-dominant mixtures for E/N from 40 to 80 Td. The effect of these electron-impact processes was specific for each of the studied parameters.     

Mikrophysikalische Bestimmung elektronenkinetischer Kenngrößen im binären Molekül-Mischplasma von Stickstoff und Wasserstoff I. Geschwindigkeitsverteilungsfunktion,Transportgrößen und Stoß-frequenzen für Dissoziation und Direktionisation im Mischplasma

For the low ionized anisothermal plasma in a mixture of moleculare nitrogen and molecular hydrogen the isotropic part of the velocity distribution function of the electrons is calculated and compared with the experimentally determined velocity distribution. the calculation of this distribution is performed by the help of the homogeneous and stationary electron Boltzmann-equation and takes into consideration all essential collision processes between the electrons and the N₂ and H₂ molecules. Furthermore, the calculated results of the mean energy, of the transport coefficients, of the collision frequencies for dissociation and direct ionization of the molecules, of the first Townsend coefficient of the molecules and of the collision rates for the direct ionization of the N- and H-atoms in the mixture are represented for the range 6–100 V/(cm Torr) of the reduced electric field strength and for any composition of the N₂-H₂ mixture.     

Atmospheric interaction radiation from high altitude rocket exhausts

A model for calculating the infrared radiation from rocket exhaust gases at high altitudes (typically above 200 km), caused by collisions between exhaust molecular species and atmospheric species is presented. At altitudes where the atmospheric mean free path is larger than a typical rocket exhaust plume lenght scale, the evolution in space and time of the exhaust gases is described by the kinetic theory of gases. In addition, the collision frequency between exhaust and atmospheric species is sufficiently low that excited molecules have time, on the average, to loose thsis excitation energy via radiative emission before experiencing another collision. Thus, the distribution of excited molecular states is nonthermal in this model. Two examples of such radiation are presented: one for the radiation from the CO₂ (υ₃) mode and the other for the H₂O(υ₃) mode. The atmospheric collision partner for excitation of both of these exhaust species is taken to be atomic oxygen, the dominant atmospheric constituent at high altitudes.     

Kinetic Description of the Stationary Band-Like Weakly Turbulent Beam Discharge Plasma in Hydrogen. I. Basic Equations — Numerical Approach — Ionization and Dissociation Budget

On the basis of the electron Boltzmann equation and of the balances for the charge carriers (e, H⁺, H₂⁺, H₃⁺), the H-atoms and the metastable H(2s)-atoms for the H/H₂-mixture the behaviour of the weakly turbulent, band-like electron-beam discharge plasma in hydrogen has been calculated taking into account the main collision and transport processes. In dependence of the normalized discharge length, the life time of the neutral particles in the band-like plasma and the electron beam generated turbulence energy density the ionization and dissociation budget and in particular the most important electron-heavy particle collision rates, which appear in the balance equation system, are investigated in the present part of our paper. In a second part the results related to the budget of the ions and the metastable atomic state will be reported and an analysis of the main processes in the balances will be made.     

Vibrational coordinates in the electron jump model

The role of quantization of vibrational coordinates in the electron jump model of alkali atom, dimer plus halogen molecule collisions is examined. Despite the bound states of the molecule ions involved, a classical approximation may offer good approximation over a wide collision energy range for the energy distributions of the ions in a single electron jump. Some results are calculated for K + Br₂ and K₂ + Br₂. The theory assumes that the electron jump probability is governed by the electronic matrix element H₁₂ alone. Elementary arguments are offered to suggest that this may be a reasonable approximation.     

Ion-electron coincidence study of the thermal He(23S) + H2 Penning reaction

A new Penning-electron-Penning-ion coincidence method is described. It is applied to the study of the thermal reaction of He(2³S) with H₂. The main results reported are separate electron energy spectra that are coincident with the three different ions formed: HeH₂⁺, HeH⁺ and H₂⁺. Based on these results it is shown that the Penning reaction of the He(2³S)/H ₂ system proceeds in two well-separated steps: (i) ionization at distances R (HeH₂) ? 6a₀ in which H₂⁺ (v) is formed in different vibrational states; and (ii) reactive collision of H₂⁺ (v) with He. For the second step the variation of the branching ratios with vibrational quantum numbers v = 0 to v = 10 is derived, and it is shown that these branching ratios may be regarded as relative vibrational-energy-dependent cross-sections for the collision of H₂⁺ (v) with He at an average relative kinetic energy of ～20 meV.     

Der Einfluß der Stoßkenndaten auf die Elektronenkinetik in schwachionisierten Mischplasmen

The Influence of the Characteristic Quantities of the Collision Processes on the Electron Kinetics in the Low Ionized Mixture Plasm Starting from former investigations concerning the electron kinetics in the pure molecular plasma of N₂ and H₂ and in the mixtures of N₂/Ne and N₂/H₂ the influence of the important characteristic quantities of the collision processes on the isotropic distribution function and the energy balance of the electrons was studied for binary mixtures. The conclusions obtained were verified by results calculated numerically for the energy balance in the three mixtures He/Ne, N₂/H₂ and N₂/Ne which were investigated in the relevant range of the normalized electric field strength E/p₀ as a function of the mixture ratio. This analysis demonstrates the sensitive dependence of the macroscopic properties of the binary mixtures on the characteristic quantities of the collision processes of the electrons with the two components of the binary mixture.     

Vibrational inelastic electron-H<Subscript>2</Subscript> scattering revisited: numerically converged coupled channels space frame calculations with model interactions

The collisional excitation of the lower vibrational levels of H₂(¹Σ_g⁺) molecules by low-energy electron impact is computed using an empirical model potential and by solving the coupled-channels scattering equations within a space-fixed (SF) frame of reference formulation. Numerically converged partial, integral inelastic and elastic cross-sections are obtained from what is an essentially exact treatment of the dynamics and the results are compared with measurements and with earlier calculations on the same system. The usefulness of the SF method for handling excitation processes at near-threshold collision energies is discussed and analyzed through the calculations of collisional superelastic partial cross-sections down to 10^-2 meV of collision energy.     

On the theory of surface impedance of metals placed in a magnetic field

The smooth non-monotonous dependence of the metal surface impedance upon the magnetic field H is investigated theoretically for the cases of diffuse and specular reflection of electrons from the specimen boundary. The type of the electron-surface interaction has been found to have very little effect on the magnitude of the impedance Z_α(H) in the range of weak magnetic fields [equation (1)]. In a strong field [equation (2)] the surface impedance behaves differently for diffuse and specular reflection. The form of the Z_α(H) function depends essentially on the ratio of the electromagnetic wave frequency ω and the collision frequency of electrons ν. This provides a possibility of establishing experimentally the frequency of electron collisions with volume scatterers.     

He2+离子和H2,O2分子碰撞过程中电子俘获和靶激发的发射截面

实验结果表明:在He²⁺和H₂,O₂碰撞过程中存在着双电子俘获而产生激发态的过程,同时也存在着单电子俘获而产生激发态的过程。在靶H₂,O₂直接激发过程中,测量到了巴耳末系H_α,H_β,H_γ和OI的发射谱。本文给出随入射离子速度变化的Hel,Hell和H_α,H_β,H_γ,O 关键词：     

Pathways in the molecular fragmentation for the C2H5OH/He electrical discharge

ABSTRACT

This study focuses on the glow discharge generated with a gases mixture of Ethanol (C₂H₅OH) and Helium (He), at different concentrations maintained at a total pressure of 2.0 Torr. We used optical emission spectroscopy (OES) to analyze the discharge mixture at different concentrations of Helium. Single Langmuir probe data was used to determine the Electron Energy Distribution Function (EEDF). For the total C₂H₅OH/He mixture plasma concentrations, the EEDF has a Maxwellian distribution function. A decrease in He concentration results in significant changes in the EEDF, this behavior is related to the increase in the C₂H₅OH percentage must increase the energy loses of the electrons in the inelastic collision with C₂H₅OH producing a significant change in the EEDF, therefore, the EEDF pattern results in an increase of electron–molecule reaction rates. The rise in electron temperature for increasing Helium percentage is explained by the decreasing electron energy loss in the inelastic collisions with C₂H₅OH molecule. It observes a decrease of electron density ne as a function of the Helium percentage, which can be related to the ratio between ionization cross sections of Helium and C₂H₆O molecule. The active species are generated in the electron-molecule processes, which are associated with electron impact dissociation of C₂H₅OH and Helium electronic impact excitation in the gas phase. The emission optical spectra (OES) show changes in the intensity of the most important peaks of the plasma mixture, which indicates the dependence in the formation of the plasma as a function of the percentage of the gases. The changes in the intensities of the same observed species are due to different processes of excitation and ionization energies of the system, in addition to the increase of He metastable states He I. Hydrogen is the main product obtained from the decomposition of C₂H₅OH.     

Absorption of electromagnetic energy by slow electrons under scattering from Coulomb centers

Simple analytical expressions are obtained for the rate of the inverse stimulated bremsstrahlung absorption under electron scattering from a Coulomb center with charge Z in the presence of the electromagnetic field. The initial and final values of electron energy are assumed to be small compared to the Rydberg energy Z ² (atomic units are used throughout). Single-photon processes of absorption and induced radiation of photon by electron are treated. It is assumed that the electromagnetic field frequency ω is rather low, so that the condition Zω/p ³ ? 1, where p is the electron momentum, and the condition ?ω ? p ² are valid. However, this frequency is assumed to be fairly high compared to the electron-Coulomb center collision frequency: ω ? v _nei. The dependences of the rates of photon absorption and induced radiation on the angle θ between the direction of incident electron and the electromagnetic field polarization vector (assumed to be linearly polarized) are obtained. It is demonstrated that, for any angles θ, the rate of photon absorption is higher than the rate of induced radiation and, therefore, the Marcuse effect for slow electrons (electromagnetic field amplification) is absent. It is further demonstrated that a slow electron on the average absorbs double ponderomotive energy per collision with an ion (Coulomb center) in Maxwellian plasma. This agrees both with the known results calculation for fast electrons and with the known results of the calculation based on the classical Boltzmann kinetic equation for plasma.     

The Impact of Different CO Admixtures on the Electron Kinetics in Collision Dominated RF He/CO Bulk Plasmas

Electron energy distribution functions and mean collision frequencles for the uniform bulk plasma of established rf discharges in He/CO have been obtained by solving the time dependent Boltzmann equation. The results, which are of importance for plasma processing and laser technology, show that already small CO admixtures to He remarkably changes the periodic behaviour of the energy distribution of the electrons by drastical enhancement of the collisional energy dissipation effectiveness in the mixture. These changes can be interpreted on the basis of a lumped energy dissipation frequency in all electron collisions which is determined by the atomic data of the electron collision processes as well as by the admixture fractions and which drastically increases with increasing CO admixture. The degree of modulation of the energy distribution in different parts of the electron energy space and its population on the time average at higher energies are determined by the relation between the rf field frequency and the mentioned lumped energy dissipation frequency.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

Effect of electron-neutral collisions on the satellites of the Thomson scattering spectrum in arc plasmas

The effect of electron-neutral collisions on the high frequency spectrum of laser radiation scattered by the free electrons of a plasma is investigated for a partially ionized H₂ are plasma at atmospheric pressure. The calculations are carried out along Gorog's theory solving the linearized Boltzmann equation for electrons with a collision term. The collision integral is approximated by a Krook relaxation model with the collision frequency determined from experimental electron-atom scattering data. The collisions influence size, half width, and position of the high frequency satellites. In a H₂ arc plasma, the change of the satellites' position is negligible as well as the change in half width within experimentally attainable error limits. The change of size is of minor importance, since the general evaluation procedure uses only normalized scattering intensities. Thus, for laser scattering experiments in are plasmas the collision-free theory can be applied.     

Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

Quantum rotational scattering of H2 and its isotopologues with He

Quantum close-coupling computations of the rotational quenching of H₂ and its isotopologues due to He impact are performed using a highly accurate potential energy surface. State-to-state cross sections are obtained in a wide range of collision energies between 10^?5 cm^?1 and 10⁴ cm^?1, and the theoretical rate coefficients are reported for temperatures ranging from 10^?4 K to 3000 K. Compared with previous studies, the well depth of the potential adopted in this study is larger, leading to stronger resonance effects in the cross sections of He-HD. The accurate potential was employed to investigate the isotope effects of H₂ in detail. The cross-section resonances shift towards lower collision energies and become stronger with increasing reduced mass. The calculated cross sections and rate coefficients of H₂ and its isotopic variants in collisions with He are provided to study the energy transfer in these systems.     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.