Features of kinetic processes in the active medium of a pulsed chemical oxygen-iodine laser

Conclusion It can be concluded from our experiments and calculations that the product CF₃O₂ of the interaction between the CF₃ radical and the O₂ molecule quenches the oxygen O₂(¹) more strongly. At low chlorine admixture density in the singlet-oxygen stream this output energy of the oxygen-iodine laser with CF₃I as the atomic iodine donor is lower compared with CH₃I. The rate constant of quenching singlet oxygen by CF₃O₂ molecules is (3–5)·10^–11 cm³·sec^–1. It would be possible to decrease the influence of CF₃O₂ by adding to the initial O₂ ^*–O₂–CF₃I–Ar active mixture some other substance causing the CF₃ radicals to enter in a chemical reaction with a shorter characteristic time than that for CF₃O₂ formation. Of course, neither the initial substance nor the reaction products should quench O₂ ^* noticeably. This role can be possibly assumed by the NO molecule.The influence of the chlorine additive on the output energy of a laser with CH₃I and CF₃I differs greatly. The choice of the chlorine donor must therefore be determined by the amount of this additive. CH₃I is preferable if the chlorine is fully utilized in the singlet-oxygen laser, and CF₃I in the opposite case.Quantum Radiophysics Division, Lebdev Physics Institute. Translation of Preprint No. 21 of the Lebedev Physics Institute, Moscow, 1991.     

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

A spray type of singlet oxygen generator for driving the Chemical Oxygen-Iodine Laser was developed. Singlet oxygen, O₂(¹Δ_g), is generated by a fast reaction of chlorine with basic hydrogen peroxide solution in the form of a dense spray. A mathematical model of this reaction system showed that O₂(¹Δ_g) can be generated in this system with a high yield (0.70–0.80), high utilization of chlorine (0.75–0.95), and effective utilization of liquid (0.36–0.54) at very high generator pressures (35–75 kPa). Experimental studies of this reaction system without an efficient separation of liquid proved an efficient O₂(¹Δ_g) production characterized by a rather high product of chlorine utilization and O₂(¹Δ_g) yield (0.4–0.9) at very high generator pressures (30–80 kPa). This pressure is much higher than the operation pressure used in other generators, which should be beneficial for a pressure recovery system of the COIL. These results provided the basis for designing a centrifugal spray generator with an efficient separation of liquid from the gas flow, which is the subject of the following paper.     

密度泛函理论方法研究6H-SiC(0001)表面对氧分子和水分子的吸附

本文通过密度泛函方法计算6H-SiC(0001)表面对氧分子和水分子的吸附. 在6H-SiC(0001)表面上吸附的O₂分子自发地解离成O^*,并被吸收在C与Si原子之间的空位上. 吸附的H₂O自发地分解成OH^*和H^*,它们都被吸附在Si原子的顶部,OH^*进一步可逆地转化为O^*和H^*. H^*可以使Si悬键饱和并改变O^*的吸附类型,并进一步稳定6H-SiC(0001)表面并防止其转变为SiO₂.     

Refocussing of chemical and paramagnetic shift anisotropies in 2H NMR using the quadrupolar-echo experiment

A simple two-pulse spin-echo experiment is shown to refocus inhomogeneous broadening arising from both chemical and/or paramagnetic shift anisotropy and a first-order I=1 quadrupolar interaction. The method is shown to yield ²H NMR spectra of a paramagnetic solid (CuCl₂ · 2D₂O) and of a non-paramagnetic solid (D₂C₂O₄ · 2D₂O) that are significantly less distorted than those provided by the conventional quadrupolar-echo method. The technique will thus prove useful in studies of motion and dynamics where detailed analysis of the ²H lineshape is performed.     

T*相超导体(Bi,Sr)2(Y,Ce)2Cu2Oy的性质研究

研究了T^*相超导体（Bi，Sr）₂（Y，Ce）₂Cu₂O_y的成相规律，发现缓冷对T^*相单相样品的制备是有利的．淬火样品的主相物质为Ce₂Y₂O₇，完全不含T^*相结构．在室温到熔化温度的范围，热分析未观察到结构相变．在240—460℃，相对每个Cu原子超导体失氧约0.1个氧．氧气中烧结并缓冷到室温的样品在30K出现零电阻现象 关键词：     

Feasibility Study on Quantitative Measurements of Singlet Oxygen Generation Using Singlet Oxygen Sensor Green

The purpose of this study is to investigate the feasibility for quantitative measurement of singlet oxygen (¹O₂) generation by using a newly developed ¹O₂-specific fluorescence probe Singlet Oxygen Sensor Green reagent (SOSG). ¹O₂ generation from photoirradiation of a model photosensitizer Rose Bengal (RB), in initially air-statured phosphate buffered saline (PBS) was indirectly monitored with SOSG. In the presence of ¹O₂, SOSG can react with ¹O₂ to produce SOSG endoperoxides (SOSG-EP) that emit strong green fluorescence with the maximum at 531 nm. The green fluorescence of SOSG-EP is mainly dependent on the initial concentrations of RB and SOSG, and the photoirradiation time for ¹O₂ generation. Furthermore, kinetic analysis of the RB-sensitized photooxidation of SOSG is performed that, for the first time, allows quantitative measurement of ¹O₂ generation directly from the determination of reaction rate. In addition, the obtained ¹O₂ quantum yield of porphyrin-based photosensitizer hematoporphyrin monomethyl ether (HMME) in PBS by using SOSG is in good agreement with the value that independently determined by using direct measurement of ¹O₂ luminescence. The results of this study clearly demonstrate that the quantitative measurement of ¹O₂ generation using SOSG can be achieved by determining the reaction rate with an appropriate measurement protocol.     

Centrifugal spray generator of singlet oxygen for a chemical oxygen-iodine laser

A centrifugal spray generator of singlet oxygen, O₂(¹Δ_g), for driving a chemical oxygen-iodine laser was developed and its operation was experimentally studied. Modeling of the liquid separation from the gas flow showed that the separator designed could remove droplets larger than 0.5 μm from gas, which is very important for the laser operation. This result was confirmed by experiments. Experimental studies proved that O₂(¹Δ_g) could be produced with a high efficiency (chlorine utilization 0.68–0.87 and O₂(¹Δ_g) yield 0.35–0.7) even at very high generator pressures (25–70 kPa), which cannot be attained by other O₂(¹Δ_g) generators.     

喷射型单重态氧发生器性能研究

单重态氧发生器作为氧碘化学激光的核心部件,为化学激光器提供化学能。通过对工业喷射器及旋风分离器的研究,结合产生单重态氧的化学反应环境,进行了大量模拟及设计改进工作,研制了一种新型喷射型单重态氧发生器,并进行了相关实验研究。喷射型单重态氧发生器利用喷嘴能够产生比传统发生器类型更多的气液表面,获得足够的反应效率,可以大幅度降低发生器液体使用量,从而减小发生器辅助系统,提高体积效率。为满足O2（1）停留时间短及分离效率高的要求,利用气液两相喷射的高初速度以旋风分离器完成气液分离。新型发生器氯气利用率可达97%~99%,其O2（1）产率为40%~50%。     

硫代碱基与单态氧反应速率常数的时间分辨光谱测定

硫代碱基作为一类免疫抑制性药物被广泛关注,由于硫原子的取代,硫代碱基可以吸收UVA波段紫外光,并通过系间窜越至激发三重态敏化氧气生成广泛应用于光动力学治疗的活性氧物质单态氧(~1O_2).然而,硫代碱基容易与自身敏化产生的~1O_2氧化发生反应,导致光毒性.在已有关于硫代碱基与~1O_2反应机理的研究基础上,本文采用瞬态光谱方法直接测得~1O_2在1270 nm处磷光信号的衰减动力学,得到硫代碱基与单态氧反应的速率常数.通过比较6-硫代鸟嘌呤、4-硫代尿嘧啶、2,4-二硫代尿嘧啶分别在水、乙腈以及二者混合溶剂中与~1O_2的反应,发现硫代碱基与单态氧反应速率常数受溶剂的极性影响.随着溶剂极性增大,反应速率常数则减小.此外,通过对比研究,发现硫代嘧啶类碱基与~1O_2的反应速率小于硫代嘌呤类碱基,说明在光动力学治疗中以硫代嘧啶类药物作为光敏剂是较为合适的选择.     

Wide-band exciplex halogen lamps operating on inert gas mixtures with chlorine and Freon-12 molecules

The results of analysis of the spectral characteristics of short-wave radiation sources operating on transitions in argon, krypton, and xenon monohalogenides, as well as chlorine molecules, excited by a longitudinal low-pressure glow discharge are considered. Radiation emitted by ArCl^*, KrCl^*, XeCl^*, Cl ₂ ^** , and Cl ₂ ^* molecules in a spectral range of 170–350 nm is optimized using complex working mixtures of Ar-Kr-(Xe)-Cl₂ in the lamps. The average radiation power of the lamps ranges from 1 to 10 W for an efficiency of ≤25%. Optimization of wide-band lamps on transitions in chlorine molecules and the decay products of Freon-12 molecules (CF₂Cl₂) is carried out on mixtures of helium with chlorine and Freon-12 molecules. This makes it possible to develop lamps emitting in a spectral range of 140–270 nm and containing no costly inert gases (Xe or Kr) in their working mixtures. Exciplex halogen lamps with a wide-band emission spectrum in the VUV-UV range can be used in spectrometers as radiation sources in experiments with absorption and in high-energy chemistry, ecology, and medicine.     

Study of the oxygen incorporation and diffusion in Sr(Ti0.65Fe0.35)O3 ceramics

For applications in high temperature fast conductometric gas sensors and oxygen membranes, several mixed conductors show promising features. In particular, acceptor-doped strontium titanate (STO) has been widely investigated for an application as a fast conductometric oxygen sensor. By a B-site substitution with 35% iron, the resulting ceramic solid solution SrTi_0.65Fe_0.35O₃ (STF35) exhibits a temperature-independent conductivity, an ideal prerequisite for a gas sensor.In the presented study, the oxygen tracer exchange behavior and the tracer diffusion of dense ceramic STF35 bulks have been investigated in the temperature range between 600 and 900 °C by means of ¹⁸O₂ tracer exchange experiments and subsequent secondary ion mass spectrometry (SIMS), resulting in the determination of k* and D* values, respectively.Furthermore, by coating the samples with a thin alkaline earth metal oxide layer (CaO), a significantly enhanced oxygen surface exchange reaction was observed. These findings are in good agreement with previous results on STO single crystals.     

Anion dependence of the valence state detrapping behavior for a fused hydrocarbon bridged binuclear mixed valence iron compound and its di-oxygen sensitivity

Monocationic forms of the symmetric and asymmetric indacene bridged species [(Cp^*Fe)₂(-s-indacene)],I, and [(Cp^*Fe)₂(-as-indacene)],II, are fully detrapped and trapped, respectively, over the entire range from 1.5 K to ambient temperature as their BF ₄ ^– salts. In contrast to [II ⁺][BF ₄ ^– ], the TCNE^.– salt [II ⁺][TCNE^.–] exhibits a transition from fully trapped to a largely detrapped valence state behaviour over the increasing temperature range 100 to 300 K. Mössbauer spectra ofI suggest that while it is relatively insensitive to oxygen as a neat solid, it is strongly oxidized by O₂ in dry hexane solution. Similar studies ofII indicate essential insensitivity to O₂, both as a solid and in hexane solution.     

ARC study of the oxygen Schumann-Runge system

Other investigations have shown that the Schumann-Runge system of oxygen is excited by an inverse predissociation mechanism, O + O→ O^*₂. Under the condition where this excitation mechanism dominates, there is some question as to whether the radiation yielded a true rotational/vibrational electronic band spectrum, as opposed to a recombination continuum. Furthermore, there is controversy as to whether the spectral intensity is that given by equilibrium theory. The present work utilized a 1 atm arc jet facility to heat air and O₂-noble gas mixtures to temperatures between 3000 and 3500°K. Both photographic and photoelectric spectra were recorded. In the latter case, wavelength scans from 2000 to 6000 Å were carried out with 5 Å resolution to obtain absolute intensity data. The spectra were found to have true rotational/vibrational electronic band structure, and were identified as the O₂ Schumann-Runge ssytem. Comparison with an equilibrium radiation model showed excellent agreement. A slight adjustment was made in the electronic transition moment for the NO(β) system as demanded by the air runs.     

An improved method for preparation of Ce<Subscript>0.8</Subscript>Pr<Subscript>0.2</Subscript>O<Subscript>Y</Subscript> solid solutions with nanoparticles smaller than 10 nm

Ce_0.8Pr_0.2O_Y solid solutions with ultrafine crystalline sizes and high specific surface area were prepared by an improved citrate precursor method, where a nitrogen treatment was added prior to calcinations in air. The samples were characterized by TG-DSC, Raman spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET nitrogen adsorption. XRD and Raman results show that the formation of Ce_0.8Pr_0.2O_Y solid solutions typical of the fluorite-like cubic structure with oxygen vacancies occurs when the Ce–Pr citrate precursors are heated at high temperature in the nitrogen atmosphere. Subsequent calcinations at a low temperature in air to remove carbon species have no apparent effects on the formed solid solutions. Ce_0.8Pr_0.2O_Y solid solution prepared by the improved citrate precursor method at 800°C has ultrafine nanoparticles of less than 10 nm and high specific surface area of 92.1 m²/g, while the sample prepared by the conventional citrate precursor method has mean particle size of 62.1 nm and specific surface area of 18.1 m²/g. Furthermore, Ce–Pr solid solution by the improved method have the mesoporous structure, more lattice defects and oxygen vacancies, which will have a promising application in the catalyst region as well as SOFC field.     

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.     

Role of defects in magnetic properties of Fe-doped SnO2 films fabricated by the Sol--Gel method

This paper obtains the room temperature ferromagnetism in Sn1 xFexO2 films fabricated by the Sol-Gel method.X-ray diffraction results show that Fe doping inhibits the growth of SnO2 and Fe3+ ions occupy the Sn sites.The measurement of resistance excludes the free carrier inducing ferromagnetism.Moreover,the temperature dependence of magnetization has been better fitted by the Curie-Weiss law and bound magnetic polaron(BMP) theory.An enhancement of ferromagnetism is achieved by annealing the samples with x = 7.1% in H2,and a decrease of oxygen flow rate.All these results prove that the BMP model depending on defects can explain ferromagnetism in diluted magnetic oxides.     

Electronic structure of α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Ab initio simulations and comparison with experiment

Al₂O₃ films 150 Å thick are deposited on silicon by the ALD technique, and their x-ray (XPS) and ultraviolet (UPS) photoelectron spectra of the valence band are investigated. The electronic band structure of corundum (α-Al₂O₃) is calculated by the ab initio density functional method and compared with experimental results. The α-Al₂O₃ valence band consists of two subbands separated with an ionic gap. The lower band is mainly formed by oxygen 2s states. The upper band is formed by oxygen 2p states with a contribution of aluminum 3s and 3p states. A strong anisotropy of the effective mass is observed for holes: m _h⊥ ^* ≈ 6.3m ₀ and m _h‖ ^* ≈ 0.36m ₀. The effective electron mass is independent of the direction m _e‖ ^* ≈ m _e⊥ ^* ≈ 0.4m ₀.     

Inter- and intra-crystalline ion-exchange equilibria in the system FeCrAlO

The tie lines delineating ion-exchange equilibria between FeCr₂O₄FeAl₂O₄ spinel solid solution and Cr₂O₃Al₂O₃ solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr₂O₃Al₂O₃ solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO₂ and Y₂O₃ThO₂ electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.     

电子束引起的残余含氧气体在镍(001)面上的吸附

当一束具有一定能量和强度的电子束轰击超高真空系统中残余的水汽、一氧化碳和二氧化碳时,将导致这些气体分子通过如下反应:H₂O→O_ad+H₂,CO₂→O_ad+CO,CO→O_ad+C_ad分解并共吸于镍表面。碳和氧的原子各自占据镍(001)面部份四重吸附位置,形成结构为p(2×2)或c(2×2)的许多独立的吸附畴,电子束轰击促进畴的成核、长大、连结和有序化。当氧和碳的原子占据了镍(001)面约一半的四重吸附位后,上述吸附反应将与导致氧和碳的脱附反应:C^*+O_ad→CO,O^*+C_ad→CO平衡,氧化镍与碳化镍开始成核。由于残余含氧气体中氧的含量超过碳,氧化镍成核占优势,使碳的吸附被排斥,已吸附的碳被排挤,形成电子束斑内氧高碳低、束斑外碳高氧低的“互补”分布。电子束轰击过程中碳的俄歇峰形的变化反映着碳原子与基底原子的不同结合状态。电子束的解离效应在吸附的初始阶段起重要作用,而其热效应对氧化镍的长大起重要作用。 关键词：     

PrBa2Cu3O7-δ的制备和电子结构

采用固相反应法制备了正交单相PrBa₂Cu₃O_7-δ样品.运用标准直流四引线法测量了该样品的电阻,发现它随温度的变化呈半导体行为.通过XPS测量表明,样品中明显合有Pr⁴⁺.最后从能带结构讨论了PtBa₂Cu₃0_7-δ不超导的原因. 关键词：