Field ionization of ozone

Experimental results on the field ionization of ozone at an iridium surface using a magnetic sector atom-probe FIM show that at the lowest field of ~1.5 V/Å only 25% of all ions produced are O⁺₃, while O⁺₂ and a small percentage of O⁺ indicate field induced dissociation of ozone and recombination of atomic oxygen into O₂. At high fields and free space ionization, O⁺₂ is predominant, while the atomic oxygen as a dissociation product escapes without being ionized and cannot be detected. Using pure oxygen as an imaging gas in the FIM, O⁺₂ ions do not dissociate under the same conditions.     

Non Equilibrium Vibrational Population and Dissociation Rates of Oxygen in Electrical Discharges: The Role of Atoms and of the Recombination Process

The influence of oxygen atoms on the population densities of vibrational levels of molecular oxygen has been studied for discharge conditions in which the atoms come 1) from electronic transitions to Herzberg and Schumann systems 2) from the pure vibrational mechanism (PVM) discussed in Chem. Phys. 30 (1978) 95. In the first case the atoms deactivate the first vibrational levels of O₂, thus reducing the vibrational temperature and the propagation of the introduced vibrational quanta by V — V exchanges. Under these conditions PVM disappears. An assisted recombination dissociation mechanism, however, holds in these conditions, due to the recombination process which induces a strong disequilibrium on the levels near to the dissociation continuum. These levels can redissociate by collisions with heavy particles. The results of pure vibrational mechanism in the presence of atoms are very similar to those discussed in our previous work. The production of oxygen atoms self adjusts to small values due to the increased importance of V — T deactivation by oxygen atoms.     

Electron kinetics in dc CF4 + O2 mixture discharge

The electron distribution function, transport coefficients and rate coefficients for the dissociation of CF₄ and the excitation of a¹ _g and b¹ _g ⁺ states of oxygen have been calculated for a CF₄ + O₂ mixture discharge. The two-term approximation was used in solving the electron Boltzmann equation. The influence of the dissociation was ignored, so that the results are parametric in the density reduced electric fieldE/N and the ratio of the mixture components. Only slight dependence of the calculated quantities on the composition of the gas mixture has been observed. The critical electric field for the onset of the discharge was found to beE/N=1.1–1.25 × 10^–15 Vcm² and it is weakly decreasing with growth of the oxygen content. With a small amount of oxygen added to CF₄ the electron distribution function and the mean kinetic energy remain practically unchanged.     

Reduced Graphene Oxide decorated with Manganese Cobalt Oxide as Multifunctional Material for Mechanically Rechargeable and Hybrid Zinc–Air Batteries

Spinel MnCo₂O₄ nanoparticles on nitrogen‐doped reduced graphene oxide (MnCo₂O₄/NGr) are synthesized for advanced zinc–air batteries with remarkable cyclic efficiency and stability. The synthesized MnCo₂O₄/NGr exhibits good oxygen‐reduction reaction (ORR) activity with half‐wave potential E _1/2 of 0.85 V (vs reversible hydrogen electrode (RHE)), comparable to commercial Pt/C with E _1/2 of 0.88 V (vs RHE) along with superior oxygen electrode activity ΔE = 0.91 V for the ORR/OER (oxygen‐evolution reaction) in alkaline media. Durability tests confirm that MnCo₂O₄/NGr is more stable than Pt/C in alkaline environment. MnCo₂O₄/NGr functions with stable discharge profile of 1.2 V at 20 mA cm^?2, large discharge capacity of 707 mAh g^?1_Zn at 40 mA cm^?2 and a high energy density of 813 Wh kg^?1_Zn in a mechanically rechargeable zinc–air battery. The electrically rechargeable MnCo₂O₄/NGr zinc–air battery displays hybrid behavior with both Faradaic and oxygen redox charge–discharge characteristics, operating at higher voltage and providing higher power density and excellent cyclic efficiency of 86% for over 100 cycles compared to Pt/C with efficiency of around 60%. Moreover, hybrid zinc–air battery operates with a stable and energy efficient profile at different current densities.     

Intensification of shock-induced combustion by electric-discharge-excited oxygen molecules: numerical study

Mechanisms of combustion enhancement in a supersonic H₂–O₂ reactive flow behind an oblique shock wave front are investigated when vibrational and electronic states of O₂ molecule are excited by an electric discharge. The analysis is carried out on the base of updated thermally nonequilibrium kinetic model for the H₂–O₂ mixture combustion. The presence of vibrationally and electronically excited O₂ molecules in the discharge-activated oxygen flow allows to intensify the chain mechanism and to shorten significantly the induction zone length at shock-induced combustion. It makes possible, for example, to ignite the atmospheric pressure H₂–O₂ mixture at the distance shorter than 1 m behind the weak oblique shock wave at a small energy E_s = 1.2 × 10^–2 J · cm^–3 input to O₂ molecules. At higher pressure it is needed to put greater specific energy into the gas in order to ignite the mixture at appropriate distances. It is shown that excitation of O₂ molecules by electric discharge is much more effective for accelerating the hydrogen–oxygen mixture combustion than mere heating the gas.     

Experimental Study and Modelling of Formation and Decay of Active Species in an Oxygen Discharge

A microwave (2.45 GHz) oxygen discharge (3 hPa, 150 W, 50 mL.min^–1) is studied by optical emission spectroscopy of O(⁵P) (line 777.4 nm) and of the atmospheric system of O₂(head‐line 759.4 nm). Calibration of the spectral response of the optical setup is used to determine the concentrations of O(⁵P) and O₂(b). The concentration of the O(⁵P) atoms is in the range 108–109 cm^–3 and the concentration of the O₂(b) molecules is in the range 10¹⁴ – 2 × 10¹⁴ cm^–3 along the discharge tube. An attempt is made to simulate the experimental results by using coupling the Boltzmann equation, homogeneous energy transfer V‐V and V‐T, heterogeneous reactions on the walls (energy transfer and recombination of atoms) and a kinetic scheme (electronic transfer and chemical reactions). The Boltzmann equation includes momentum transfer, inelastic and superelastic processes and e‐e collisions. V‐V and V‐T transfer equations are obtained from the SSH theory and the kinetic scheme includes 65 reactions with 17 species [electrons e, ions O^– and O₂^–, fundamental electronic neutral species O(³P), O₂, O₂(X,v), O₃ and excited neutral species O₂(a), O₂(b), O₂(A), O(¹D), O(¹S), O(⁵P), O(4d ⁵D^o), O(5s ⁵S^o), O(3d ⁵D^o) and O(4s ⁵S^o)]. A fair agreement between experimental results and modelling is obtained with the following set of fitting values: – heterogeneous deactivation coefficient for O₂(b) γ = 2.6 × 10^–2; – rate constant of reaction [O(¹D) + O(³P) → 2 O(³P)] k₃₄ = 1.4 × 10^–11 cm³.s^–1; – electron concentration in the range 10¹⁰ – 10¹¹ cm^–3. Modelling shows that the recombination coefficient for oxygen atoms on the silica wall (range 1.4 × 10^–3 – 0.2 × 10^–3) is of the same order as the values obtained in a previous paper and that the ratio ([O] / 2 [O₂]initial) is about 33–50%. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

小尺寸VmOn+团簇的激光光解和密度泛函计算

通过激光溅射法产生了V₂O_n⁺ (n=1, 2), V₃O_n⁺ (n=1, 2, 3)和V₄O₃⁺等缺氧的钒氧团簇,并采用532和266 nm波长的激光对它们进行了光解研究. 利用密度泛函理论计算与激光光解实验相结合确定了这些团簇的几何结构和可能的光解通道. 激光光解实验表明V相似文献   

Incomplete ozone recovery effect in the presence of active oxygen species

The degree of ozone recovery after pulsed UV laser photolysis of O₂-O₃-Ar mixture is measured using time-resolved absorption spectroscopy. The effect of incomplete ozone recovery in the presence of molecular singlet oxygen O₂(a ¹Δ) and atomic oxygen is detected. This effect is caused by the reaction between the vibrationally excited ozone molecule formed due to recombination and atomic oxygen. The branching factor for the chemical channel of reaction products is γ _r = 0.81 ± 0.13.     

氧分压对Mg掺杂ZnO薄膜结晶质量和光学特性的影响

利用脉冲激光沉积技术,通过改变沉积过程中的氧气压力,在蓝宝石(0001)基片上制备了一系列ZnMgO合金.通过X射线衍射、反射和透射光谱以及室温和变温荧光光谱,对薄膜的结构和光学性能进行了系统地表征,分析了工作气压对ZnMgO合金薄膜的结晶质量及光学特性的影响.研究结果表明:随着沉积环境中氧气压力的增大,ZnMgO薄膜的结晶质量下降,富氧环境下,与蓝宝石晶格平行的ZnO晶粒的出现是导致薄膜结晶质量下降的主要原因;相对于本征ZnO,不同氧气环境下沉积的ZnMgO薄膜的紫外荧光峰均出现了不同程度的蓝移.随着工 关键词： ZnO Mg掺杂 脉冲激光沉积 薄膜生长 光学特性     

Discharged generator of singlet oxygen for oxygen-iodine laser. Transport kinetics of O2(a 1δg) and O2(b 1σ g + ) molecules and O(3 P) atoms in Ar:O2 and He:O2 flows excited by a 13.56-MHz discharge

To understand and reveal the basic physical factors providing the possibility of scaling of a discharged singlet oxygen generator (DSOG) in an oxygen-iodine laser, the production, and transport kinetics of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, as well as O(³ P) atoms, were investigated in Ar:O₂ and He:O₂ gas flows excited by a 13.56-MHz discharge in a wide range of pressures (4–40 Torr) and oxygen percentages. It is shown that the densities and transport kinetics of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) appear similar for oxygen mixtures with argon and helium in the same conditions independent of discharge mode. Compared to pure O₂, the dilution of oxygen with an inert gas allows higher energy inputs per an oxygen molecule to achieved, especially under conditions of the homogeneous discharge mode (α-mode), which gives a higher efficiency of O₂(a ¹δ_g) excitation in Ar:O₂ and He:O₂ mixtures. But the maximum attainable yield of singlet oxygen in Ar:O₂ and He:O₂ at fixed partial O₂ pressure is found to be comparable with the O₂(a ¹δ_g) yield in pure oxygen at the same pressure. The reason for this is the increased three-body deactivation of O₂(a ¹δ_g) by atomic oxygen in the mixtures because of the greater total pressure. The estimation of the rate constant of O₂(a ¹δ_g) three-body quenching by O(³ P) in Ar:O₂ and He:O₂ mixtures as (1.5 ± 0.5) × 10^?32 cm⁶/s was carried out from the analysis of transport kinetics of singlet and atomic oxygen in the discharge afterglow at high pressures exceeding ～10 Torr. A similar analysis for the lower pressures has revealed that losses both of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, and of O(³ P) atoms on the surface of the discharge tube, are determined by the density of each of the components. The obtained loss probabilities of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) on the silica surface show that the surface loss probabilities of all the species can increase noticeably under the discharge exposure. Thus, the key parameters determining the maximal O₂(a ¹δ_g) yield in the DSOG are a homogeneous volumetric mode of the discharge, energy input per oxygen molecule in this mode, and a low rate of O₂(a ¹δ_g) quenching. Just three-body quenching of O₂(a ¹δ_g) by O(³ P) limits the singlet oxygen yield with increasing pressure. The fast removal of atomic oxygen both in discharge and in the earlier afterglow could provide DSOG scaling with pressure.     

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).     

Zur O2-Dissoziation in der Gleichstromglimmentladung. Teil I Bestimmung des Dissoziationsgrades mittels der O3-Bildung an gekühlten Oberflächen

The synthesis of ozone on the surface S cooled with liquid nitrogen O + O₂·S→O₃·S[1] was used to measure the concentration of atoms in a flow tube downstream of a d.c. discharge. The flow tube was constructed in the form of a U-tube. The ozone was deposited as a blue liquid film in the neighbourhood of the surface of the liquid nitrogen on the walls of the part of the U-tube, which was connected with the discharge tube. The oxygen atom decay in the U-tube was observed by measuring the production of ozone as the distance between the discharge tube (diameter: 5,2 cm) and the surface of the liquid nitrogen was varied. The decay is first order in atom concentration for the pressures p > 1 torr. But for the pressures below p = 1 torr near by the discharge tube we observed deviations from the law of decay In [O]₀/[O] = k·t for the currents of about i = 100 mA. This effect was attributed to the process From the extrapolation of an ozone production curve atom concentrations in the discharge have been obtained. The transition from the ?H”? form to the ?T”? form (striated, low average electric field) of the discharge [2] caused the dissociation to decrease rapidly. The highest dissociation (10%) was obtained in the ?H”? form at high currents (i = 120 mA) and low pressures (p = 0,60 torr). The yield of atomic oxygen per kilowatt hour of energy was measured as functions of pressure and gas flow rate for i = 100 mA and i = 50 mA.     

Detection of oxygen atoms in a high pressure surfatron microwave discharge via two-photon four-wave mixing

3 P_J) oxygen atoms are detected in a high pressure surface wave discharge driven at 2.45 GHz via two-photon resonant degenerate four-wave mixing spectroscopy (TP-DFWM) in the forward folded BOX configuration. The nonlinear optical signal provides a direct measure of the relative oxygen atom concentration with high spatial resolution inside the discharge up to pressures of 1 bar and without distortions due to linear absorption or saturation effects. The axial distribution of oxygen atom concentration is observed to depend sensitively on total pressure and gas flux. For total gas pressures up to 600 mbar both in case of a mixture of 10% O₂/He and 10% O₂/Ar the concentration of oxygen atoms increases linearly with pressure. At higher pressures an increase with larger slope is observed for 10% O₂/Ar, while the concentration remains constant for 10% O₂/He. This is interpreted by an increase of the three-body recombination rate in O₂/He mixtures. Received: 26 July 1996/Revised version: 15 November 1996     

Efficient discharge pumping XeCl laser

Pulsed oscillation from XeCl at λ = 3080 Å has been obtained by exciting a mixture of He:Xe:BCl₃ at pressures of 1 to 7 atm with a transverse discharge. The laser efficiency relative to the discharge absorbed energy exceeds 1%. The role of dissociation recombination in the processes of excitation of XeCl¹ is discussed.     

Adsorption and dissociation of O2 on CuCl(1 1 1) surface: A density functional theory study

The adsorption and dissociation of O₂ on CuCl(1 1 1) surface have been systematically studied by the density functional theory (DFT) slab calculations. Different kinds of possible modes of atomic O and molecular O₂ adsorbed on CuCl(1 1 1) surface and possible dissociation pathways are identified, and the optimized geometry, adsorption energy, vibrational frequency and Mulliken charge are obtained. The calculated results show that the favorable adsorption occurs at hollow site for O atom, and molecular O₂ lying flatly on the surface with one O atom binding with top Cu atom is the most stable adsorption configuration. The O-O stretching vibrational frequencies are significantly red-shifted, and the charges transferred from CuCl to oxygen. Upon O₂ adsorption, the oxygen species adsorbed on CuCl(1 1 1) surface mainly shows the characteristic of the superoxo (O₂⁻), which primarily contributes to improving the catalytic activity of CuCl, meanwhile, a small quantity of O₂ dissociation into atomic O also occur, which need to overcome very large activation barrier. Our results can provide some microscopic information for the catalytic mechanism of DMC synthesis over CuCl catalyst from oxidative carbonylation of methanol.     

Reaction Kinetics and Chemical Quasi-Equilibria of the Ozone Synthesis in Oxygen DC Discharges

The spatial distribution of ozone and of oxygen atoms was studied along the active and the passive zone of a dc discharge (positive column, pressure: p = (4 … 10) · 10² Pa, current: I = 2 … 50 mA, flow rate: F = 5 … 100 sccm) in flowing oxygen. The composition of the final output O₂/O₃-mixture is controlled by relaxation processes in the passive reactor zone. It is affected sensitively by the total number density and the gas temperature in the afterglow. Steady states meaning reversible chemical quasi-equilibria were observed and analysed extensively. Within a detailed kinetic model the formation of these equilibria can be explained quantitatively. The synthesis to ozone is controlled above all by the metastable O₂ (a¹Δg) species, which modify drastically the results for the basic mechanism, considering the O atoms in the ³P and ¹D states.     

Optical characterization of atmospheric‐pressure plasma needle

The atmospheric‐pressure plasma needle is a promising source that can be used efficiently for different industrial applications. A radio frequency (RF) (13.56 MHz) generator was used to generate a He–O₂/Ar mixture plasma. The ground‐state oxygen atomic density [O] was calculated as a function of discharge parameters by “actinometry”. The Ar‐I (2p₁ → 1s₂) line at 750 nm and the O‐I (³P → ³S) line at 844 nm were used to estimate the [O] atomic density. The rotational temperature T _R of He–O₂/Ar mixture was measured from the rotational levels of the “first negative system” (FNS) by using the “Boltzmann plot”. The effect of discharge parameters on the atomic oxygen density [O] and the gas temperature was monitored. These results show that [O] density increases with RF power and O₂ concentration, but decreases with the gas flow rate. Whereas the gas temperature increases with increase in the input RF power, it decreases with increase in the gas flow rate and O₂ concentration in the mixture. Since the [O] atomic density contributes to plasma‐based biomedical applications, the proposed optimum conditions for plasma‐based decontamination of heat‐sensitive materials in the present study are 0.6% oxygen, 500 sccm flow rate, and 26 W RF power.     

Formation and photodecomposition of cationic titanium oxide clusters

In this paper we report on the titanium oxide cluster cations Ti _x O _y ⁺, generated by laser ablation of a titanium target in the region of the nozzle expansion of oxygen. The mass distribution of the clusters produced is recorded with a time-of-flight mass spectrometer. Three different series, namely TiO(TiO₂) _n ⁺ , TiO(TiO₂) _n O₂⁺, and (TiO₂) _n ⁺, appear in the spectra. Two different ablation wavelengths (infrared at 1064 nm and ultraviolet at 308 nm) are used to generate the titanium oxide clusters. At the shorter wavelength the maximum size of the clusters formed decreases. The interaction of the UV photons with the Ti _x O _y ⁺ clusters is further investigated in a separate two-laser arrangement with an IR laser for ablation and after some mm downstream with an UV system for the cluster beam irradiation. These studies indicate that the intensity of the T _x O _y ⁺ clusters with x≥4, y≥7 is strongly influenced by the absorption of UV photons. This is attributed mainly to dissociation into smaller ones.     

Positive ion mass spectra of a glow discharge in oxygen

Positive ion mass spectra in the T and H form of a glow discharge in oxygen were measured. The positive charge carriers in the T-form are O₂⁺ and O⁺, while in the H-form they are O₂⁺ only. An explanation of the discharge mechanism is proposed, based on the measured ion spectra.     

Luminescence of solids excited by adsorbed oxygen atoms

The luminescence excited upon the discharge of molecular gases O₂, N₂O, and CO onto a Zn₂SiO₄-Mn crystalline phosphor surface prefilled with oxygen atoms is studied. An interpretation of this phenomenon in terms of the model of acceleration of the surface heterogeneous recombination of oxygen atoms in the appearing adsorption layer of oxygen-containing molecules O₂, N₂O, and CO by the exchange-association mechanism is given.