Relaxing Phenomena in Negative Corona Discharge: New Aspects

Two theories, explaining the time dependence of the negative corona discharge current in air, are confronted with new experimental results. The influence of the ozone concentration on the discharge current was experimentally confirmed in dry air and in mixtures of nitrogen with oxygen. Assuming that only the dissociative electron attachment to ozone molecule is a process being responsible for a reduction of the electron component in the total mean discharge current, the mean value of the electron attachment rate constant k = (3 - 5.5) × 10^?9 cm^?3 s^?1 was derived from the measured dependence of the discharge current on the ozone concentration. The calculated value of the rate constant k corresponds to the dissociative attachment of electron to ozone molecule via process e + O₃ → products (O^? or O^?₂ negative ions).     

Isotope effects in vibrational excitation and dissociative electron attachment of DCl and DBr

The results of calculations of vibrational excitation and dissociative electron attachment cross-sections of DCl and DBr are reported. The calculations are based on the nonlocal resonance model for electron-HCl/HBr scattering. The cross-sections for many initial rovibrational target states were calculated both for the hydrogenated and the deuterated compounds. The calculations reveal an unexpected result: the vibrational excitation cross-section of the deuterated molecule may in some cases be (significantly) larger than that of the hydrogenated compound. This effect is observed when the target molecule is initially excited to a vibrational state the energy of which is close to the threshold of dissociative attachment. Rotational excitation of the target molecule plays a similar role. Isotope effects in dissociative electron attachment are also discussed.     

The short-range reaction matrix in MQDT treatment of dissociative recombination and related processes

We discuss the Lippmann-Schwinger equation which governs the short-range reaction matrix (K-matrix) in the two-step multichannel quantum defect theory (MQDT) of dissociative recombination and related processes. We show that, if the energy dependence of the electronic coupling between the dissociative state and the ionization continua can be neglected, the convergence of the Born expansion of the Lippmann-Schwinger equation is achieved at second order. For the case of energy-dependent interaction, higher order effects are tested using a non-perturbative method for solving the Lippmann-Schwinger equation. Numerical examples are given for the dissociative recombination and vibrational de-excitation of the H₂ ⁺ molecular ion.Received: 18 April 2003, Published online: 5 August 2003PACS: 34.80.Gs Molecular excitation and ionization by electron impact - 34.80.Ht Dissociation and dissociative attachment by electron impact - 34.80.Lx Electron-ion recombination and electron attachment     

CHCl3电子吸附速率常数的离子迁移谱

利用电晕放电离子迁移谱, 使用高纯氮气作为载气和迁移气体, 研究了电场强度在200～500 V/cm变化时CHCl₃的解离电子吸附速率常数, 得到样品所对应的电子吸附速率常数为1.26×10^-8～8.24×10^-9 cm³/(molecules s)．利用该装置测量了固定电场下,样品的电子吸附速率常数与样品浓度之间的关系．此外利用所获得的离子迁移谱图得到了不同电场强度下Cl^-与CHCl₃之间的离子分子反应速率常数.     

Dissociative attachment of electrons to excited molecules

The development and the first results from an experiment to carry out dissociative attachment to excited molecules are discussed. A brief summary of the relevance and status of such measurements are given. Apart from measuring the absolute cross sections from excited and state selected SO₂ molecule, we have been able to characterize the negative ion resonances using the excited state dissociative attachment. In addition, the state specificity of the electron attachment process has been used to derive information on the excited neutral state itself which has not been possible using optical spectroscopy. The applicability of this technique to other species are also discussed.     

Electron-molecule collisions at low and intermediate energies using the R-matrix method

We present the latest developments of the R-matrix method as applied to electron-molecule collisions. A variety of calculations for H₂O are presented including the study of rotational excitation and preliminary data for dissociative electron attachment. Results for the application of the recently developed molecular R-matrix with pseudostates (MRMPS) method to neutral and cationic targets are also included. This method is currently being applied to the study of collisions with anionic targets.     

Clear experimental evidence for p-wave attachment-threshold behavior in electron attachment to chlorine molecules

Using the laser photoelectron attachment method and chlorine molecules in a seeded supersonic beam, we have measured the energy dependence of the cross section for dissociative electron attachment (DA; Cl- formation) over the range 0-195 meV with an energy width of about 1 meV. Our data provide the first clear experimental evidence for p-wave behavior of a DA cross section near zero energy and are in good overall agreement with recent theoretical predictions.     

N2 production in e-beam pumped XeF lasers containing NF3

The rate of build-up of N₂ was measured in electron-beam-irradiated Ne/Xe/NF₃ mixtures using mass spectroscopy. the amount of N₂ produced indicated that N₂ is the primary nitrogen bearing stable species created in these mixtures. The rate constant for dissociative electron attachment to the NF₂ fragments produced in electron attachment to NF₃ is estimated to be 5×10^–8 cm³/s in order to explain the amount of N₂ produced.This work was supported by DARPA under Contract No. DAA01-82-C-A125 and monitored by MICOM     

Untersuchung der unelastischen Wechselwirkung langsamer monoenergetischer Elektronen mit einfachen Kohlenwasserstoff-Molekülen I.Elektronenanlagerungs-Wirkungsquerschnitte in Abhängikeit von der Elektronenenergie und vom Molekülaufbau

Investigation of the Inelastic Interaction of Slow Monoenergetic Electrons with Simple Hydrocarbon Molecules. I. Dependence of the Electron Attachment Cross Sections on Electron Energy and on Molecular Structure The formation of negative ions from a series of simple hydrocarbons was studied experimentally via an interaction of hydrocarbon molecules with monoenergetic electrons in the range of 0–15 eV. The ion formation is characterized by means of the attachment cross section in dependence on electron energy. Negative ions were formed as well by dissociative electron attachment as by direct electron attachment. The electron attachment is depending on electron energy, molecular seize, and on the number of unsaturated C-C-bonds in the molecule. The formation processes are discussed and the role of negative hydrocarbon ions in the plasma is estimated.     

Air breakdown induced by the microwave with two mutually orthogonal and heterophase electric field components

The air breakdown is easily caused by the high-power microwave, which can have two mutually orthogonal and heterophase electric field components. For this case, the electron momentum conservation equation is employed to deduce the electric field power and effective electric field for heating electrons. Then the formula of the electric field power is introduced into the global model to simulate the air breakdown. The breakdown prediction from the global model agrees well with the experimental data. Simulation results show that the electron temperature is sensitive to the phase difference between the two electron field components, while the latter can affect obviously the growth of the electron density at low electron temperature amplitudes. The ionization of nitrogen and oxygen induces the growth of electron density, and the density loss due to the dissociative attachment and dissociative recombination is obvious only at low electron temperatures.     

Compilation of Cross Section Data of Elementary Processes of HCI Applicable for Plasma Modeling

In this current work an cross section data for HCI elementary processes were calculated on the base of calculated and experimental data comparison on electrons drift rate and Townsend coefficients of dissociative attachment. Cross sections data of HCI electronic excitation are obtained for the first time.     

Functional group dependent site specific fragmentation of molecules by low energy electrons

Functional group dependence is observed in the dissociative electron attachment (DEA) to various organic molecules in which the DEA features seen in the precursor molecules of the groups are retained in the bigger molecules. This functional group dependence is seen to lead to site-selective fragmentation of these molecules at the hydrogen sites. The results are explained in terms of the formation of core-excited Feshbach resonances. The results point to a simple way of controlling chemical reactions as well as interpreting the DEA data from bigger biological molecules.     

Bond breaking and temporary anion states in uracil and halouracils: implications for the DNA bases

Low energy electrons are capable of breaking bonds in gas phase DNA bases by means of the dissociative electron attachment process. With the aid of new total scattering data in the halouracils and input from quantum chemical calculations, we describe the dipole bound and valence anion states in these compounds and present assignments for the two types of structure appearing in the cross sections. A clear distinction between the two mechanisms for bond breaking is necessary for an understanding of electron induced damage to DNA.     

Generation of cold electrons in the downstream region of a microwave plasma source with near boundary resonances for production of negative ions

A microwave driven multicusp plasma based volume negative ion source equipped with a magnetic filter is developed. Instead of employing any electrodes or current carrying filaments, microwaves of frequency 2.45 GHz is used to generate plasma by resonance heating mechanisms namely the electron cyclotron resonance (ECR) and upper hybrid resonances (UHR), occurring near the boundary plasma layers. The principal process of negative ion production in hydrogen is dissociative attachment of low energy (0.5–1.0 eV) electrons to vibrationally excited neutral molecules generated from high energy (15–20 eV) electron impact. The source therefore necessitates two distinct spatial regions (a) production and (b) attachment chambers; which would contain electrons with optimum cross section for the aforementioned processes. A biased grid after the magnetic filter further helps to lower down the electron temperature to ≤1 eV which is favorable for the dissociative attachment process.     

Dissociative electron attachment to phosphoric acid esters: the direct mechanism for single strand breaks in DNA

We use dibutyl phosphate to simulate the behavior of the phosphate group in DNA towards the attack of low energy electrons. We find that the compound undergoes effective dissociative electron attachment within a low energy resonant feature at 1 eV and a further resonance peaking at 8 eV. The dissociative electron attachment (DEA) reactions are associated with the direct cleavage of the C-O and the P-O bond but also the excision of the PO-, PO3-, H2PO3- units. For the phosphate group coupled in the DNA network these reactions represent single strand breaks. We hence propose that the most direct mechanism of single strand breaks occurring in DNA at subexcitation energies (< 4 eV) is due to DEA directly to the phosphate group.     

Collisions of Slow Electrons with Thymine Molecules

Optics and Spectroscopy - Using a hypocycloidal electron spectrometer, the total scattering cross section of slow (0–9 eV) electrons and the dissociative electron attachment cross section for...     

The influences of gas and electron temperatures on electron attachment in gas electrical discharges

Various electron attachment processes are reviewed, emphasising the way in which the rates and products of some selected reactions vary with the attaching gas temperatureT _g, the temperature,T _e, and the energy of the attaching electrons. The examples illustrating the variety of reactions are the efficient dissociative attachment reaction to CCl₄, attachment to SF₆ which involves both dissociative and non-dissociative attachment, attachment to CHCl₃ which requires activation energy, and attachment to CCl₃Br which results in both Cl- and Br- product ions. A model has been presented which is able to quantitatively explain the difference influences ofT _g andT _e on the rates of some of these reactions. Also described are the unusually efficient attachment properties of the fullerene molecules C₆₀ and C₇₀ as revealed by our FALP experiments, noting that these molecules have potential importance as efficient suppressers of electrical breakdown through gases such as those used to insulate high voltage devices. We emphasise throughout this paper the importance of an understanding of the separate influences of gas and electron temperature on attachment reactions for the modelling of practical gas discharge media such as etchant plasmas. We dedicate this paper to Professor Jan Janča on the occasion of his sixtieth birthday in recognition of his major contributions to gas discharge physics.     

Interpreting electron transmission spectroscopy and negative ion mass spectrometry data using a spherical potential well model

Experimental data obtained using electron transmission spectroscopy and negative ion mass spectrometry based on resonance electron capture are interpreted within the framework of a spherical potential well model in application to a series of chloro-and bromoalkane molecules. Allowance for the scattering of a single partial p-wave of the incoming electron makes possible (i) reproduction of the ratio of a resonance peak width to the electron energy observed in the electron transmission spectra and (ii) establishment of a relation between the total cross section of electron scattering on a molecule and the dissociative electron attachment cross section. The proposed model offers a radical simplification of the approach developed previously based on the Fashbach-Fano resonance theory.     

Threshold peak structures in the vibrational excitation of HCl by low-energy electron impact

A new model which describes dissociative electron attachment and vibrational excitation for the HCl molecule is proposed. The model is based on ab initio scattering data calculated in the fixed nuclei approximation by Morgan et al. [J. Phys. B 23 (1990) 99]. The cross sections for vibrational excitation exhibit interesting oscillatory structures in the threshold peak region.     

丝氨酸异构体的电子-分子形状共振态及其解离动力学理论研究

Shape resonances of electron-molecule system formed in the low-energy electron attachment to four low-lying conformers of serine (serine 1, serine 2, serine 3, and serine 4) in gas phase are investigated using the quantum scattering method with the non-empirical model potentials in single-center expansion. In the attachment energy range of 0-10 eV, three shape resonances for serine 1, serine 2, and serine 4 and four shape resonances for serine 3 are predicted. The one-dimensional potential energy curves of the temporary negative ions of electron-serine are calculated to explore the correlations between the shape resonance and the bond cleavage. The bond-cleavage selectivity of the different resonant states for a certain conformer is demonstrated, and the recent experimental results about the dissociative electron attachment to serine are interpreted on the basis of present calculations.