星际氧气分子的气相-尘埃模型研究（英文）

本文采用气相-尘埃模型Nautilus研究了星际氧气的演化过程,使用了两种典型初始丰度值下的恒温模型和变化物理条件下的加热模型进行模拟计算.结果表明,在冷致密云的条件下,CO、O_2和H_2O达到峰值的时间依赖于氢核密度的多少,其随氢核密度的增大而减小.在加热模型中,在温度升高后的10~5年后,氧气的丰度值与观测结果符合较好.在温度大于30 K后,氧气的稳态丰度值将不再随氢核密度而变化,且大于此温度可以阻止氧气大量的沉降到尘埃表面.此外,无论在恒温模型还是在加热模型中,低氢核密度更有利于O_2的生成.     

空气放电非平衡等离子体的模拟计算

 基于空气放电非平衡等离子体动力学,对空气放电进行了数值计算,分析了放电后等离子体中的主要粒子（N₂(v6),N₂(A3),O₂(a1),O和O₃）数密度随起始温度、电子数密度和约化场强的变化趋势。计算结果表明,随着初始温度的升高,空气放电产生的粒子数密度增加。温度为300 K时,放电产生的O原子数密度最大值约为4.90×⁷ cm^-3,而当温度升高到400 K和500 K时,O原子数密度的最大值则相应地增加到5.2×10¹⁰ cm^-3和5.51×10¹⁰ cm^-3。约化场强的影响与温度类似,其中氮气的振动激发态N₂(v6)数密度随约化场强的变化幅度不明显。电子数密度增加,粒子数密度大幅增加,氮分子的激发态N₂(A3)粒子数密度与电子数密度保持严格的线性关系。     

不同初始温度下H2/O2混合物等离子体的演化

本文对不同初始温度下,H₂/O₂混合物等离子体中主要粒子随时间发展的演化规律进行了数值模拟,得到了放电后等离子体中主要带电粒子和中性粒子密度随时间的变化规律.计算结果表明,H₂/O₂混合物等离子体中主要活性粒子密度随时间的增加减小,化学反应达到平衡所需的时间随初始温度升高逐渐减少.     

电激励O2（a1Δg）发生器的实验研究

 在纯氧，及氧气和氩气的混合气体情况下，对射频放电产生O₂（a¹Δg）进行了实验研究。射频频率为13.56MHz，额定功率500W，放电压力133.0~399.0Pa， 氧气流量最大为1.4mmol/s， 氩气流量为2.1mmol/s。研究了O₂（a¹Δg）产率随气体流量、放电气压以及混合气体放电条件的变化。O₂（a¹Δg）产率最大值约为17.5%。     

O2分子吸附的金属表面的O2(1Δg)猝灭

建立了一套流动装置测量单重态氧O₂(¹Δ_g)在O₂分子吸附的金属Cu、Cr、Ni和Ag表面的猝灭几率. 随实验时间和O₂(¹Δ_g)浓度增加,猝灭几率增加. 当上述金属样品在几帕斯卡的真空度下暴露数小时后猝灭几率会回到原先水平. 提出了一种基于表面吸附位上弱化学吸附的表面吸附氧分子O₂(¹∑_{g相似文献}   

高空核爆炸下大气的X射线电离及演化过程数值模拟

利用数值模拟程序模拟了不同高度核爆炸下大气的X射线电离及演化过程.结果表明: X射线电离产生的电子数密度在射线到达后约100 ns时刻达到峰值, 峰值数密度随着到裸核区距离的增加而减小;电子具有较长的寿命, 电子寿命随着到裸核区距离的增加而增大; X射线电离空气产生正离子O⁺, O₂⁺, N₂⁺,爆高为120 km情况下 O⁺的峰值数密度与O₂⁺的相近,能维持约1 s. X射线对空气的电离影响范围在数十千米以内,在距裸核区较近的区域, 爆高为80 km时产生的电子峰值数密度比爆高为120 km时的电子峰值数密度高, 在距裸核区较远的区域则相反.     

针状纳米MnxNi0.5-xZn0.5Fe2O4的共沉淀法制备及表征

通过在碱液中共沉淀Mn²⁺、Ni²⁺和Fe²⁺后制备了棒状的前躯体,前躯体于不同温度煅烧后制得了Mn_xNi_0:5-xZn_0:5Fe₂O₄棒状体. 利用X射线衍射仪和透射电镜对棒状体的物相、形貌及粒径进行了表征,并利用振动样品磁强计对磁性能进行研究. 结果表明长径比大于15的棒状,随着x值的增加,Mn_xNi_0:5-xZn_0:5Fe₂O₄样品的直径增加,长度下降,长径比变小,当x=0.5时其直径在50 nm左右而长径比减小到7～8. 随着x值的增加,样品的矫顽力先增加后减少,x值达到0.4时样品的矫顽力再次增加,当煅烧温度为600 oC,x=0.5时样品的矫顽力最大为134.3 Oe. 饱和磁化强度随着x值的增加先增加后减少,当煅烧温度为800 oC和x=0.2时达到最大为68.5 Oe.     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

固相反应法制备的CoxZn1-xO磁性能的研究

采用固相反应烧结法制备了Co掺杂ZnO的粉末和压片样品. XRD衍射表明样品中Co²⁺离子取代Zn²⁺离子进入了ZnO晶格中. 在室温下样品均表现为顺磁性, 利用密度泛函理论(DFT+U)方法计算得到的Co₂Zn₁₄O₁₆体系反铁磁基态更稳定, 并通过Co, O原子电子迁移变化, 表明了CoZnO体系中磁性机理更倾向于Co²⁺—O^2-—Co²⁺成键的间接交换作用模型. 改进了安德森模型中的直接交换积分J_pd公式. 提出两个可能的途径来实现具有本征铁磁性氧化物半导体.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

Cosmic deuterium

The knowledge of the primordial deuterium to hydrogen ratio provides one of the most reliable tests of the early Universe nucleosynthesis models and a direct estimate of the cosmic baryon density. Evaluations have been traditionally made using D/H estimations in the interstellar medium, extrapolated backwards in time with the use of galactic evolution models. Direct primordial D/H measurements have been carried out only recently in the direction of quasars. These measurements of deuterium abundances along with observations made in the solar system and in the interstellar medium are presented.New results that indicate spatial variations of the deuterium abundance in the interstellar medium at the level of 50% over scales possibly as small as 10 pc, may question our global vision of deuterium evolution until the causes for the origin of these variations are understood. With a conservative point of view, observations thus suggest that the primordial D/H value should be within the range 1. × 10⁻⁵−3. × 10⁻⁴, leading to a relatively low baryon content Universe.Since the actual evolution of deuterium from primordial nucleosynthesis to now is not known in details, more observations, hopefully to be made with the Hubble Space Telescope, FUSE the Far Ultraviolet Spectroscopic Explorer (launched in 1999). or from the ground with the largest telescopes (Keck, VLT,), should reveal the evolution of that key element, and better constrain its primordial abundance.     

Heterogeneous reaction mechanism of elemental mercury oxidation by oxygen species over MnO2 catalyst

MnO₂-based catalysts have attracted great attention in the field of elemental mercury (Hg⁰) catalytic oxidation because of their superior catalytic performance and wide temperature window. Quantum chemistry calculations based on density functional theory (DFT) combined with periodic slab models were carried out to investigate the heterogeneous mechanism of Hg⁰ oxidation by oxygen species (gas-phase O₂, chemisorbed oxygen, and lattice oxygen) on MnO₂ surface. The results indicate that Hg⁰ and HgO are chemically adsorbed on MnO₂ surface with the adsorption energies of ?69.50 and ?226.48?kJ/mol, respectively. The adsorption of O₂ on MnO₂ surface belongs to chemisorption. O₂ can decompose on MnO₂ surface with an energy barrier of 97.46?kJ/mol to produce two atomic adsorbed oxygen. The perpendicular adsorbed O₂ and dissociative adsorbed O₂ are more favorable for Hg⁰ catalytic oxidation than lattice oxygen, and perpendicular adsorbed O₂ is the most active oxygen for Hg⁰ oxidation. The reaction pathway of Hg⁰ oxidation by perpendicular adsorbed O₂ includes three reaction steps: Hg⁰?→?Hg(ads)?→?HgO(ads)?→?HgO. The third step (HgO(ads)?→?HgO) is endothermic by 168.17?kJ/mol with an energy barrier of 179.48?kJ/mol, and it is the rate-limiting step of the whole Hg⁰ oxidation reaction.     

The importance of OH radical–neutral low temperature tunnelling reactions in interstellar clouds using a new model

Recent laboratory experiments using a pulsed Laval nozzle apparatus have shown that reactions between a neutral molecule and the radical OH can occur efficiently at low temperatures despite activation energy barriers if there is a hydrogen-bonded complex in the entrance channel which allows the system to tunnel efficiently under the barrier. Since OH is a major radical in the interstellar medium, this class of reactions may well be important in the chemistry that occurs in the gas phase of interstellar clouds. Using a new gas-grain chemical network with both gas-phase reactions and reactions on the surfaces of dust particles, we studied the role of OH–neutral reactions in dense interstellar clouds at 10, 50, and 100 K. We determined that at least one of these reactions can be significant, especially at the lowest temperatures studied, where the rate constants are large. It was found in particular that the reaction between CH₃OH and OH provides an effective and unambiguous gas-phase route to the production of the gaseous methoxy radical (CH₃O), which has been recently detected in cold, dense interstsellar clouds. The role of other reactions in this class is explored.     

Oxygen vacancies at oxide surfaces: ab initio density functional theory studies on vanadium pentoxide

The local electronic structure at the V₂O₅ (010) surface is studied by ab initio density functional theory (DFT) methods using gradient-corrected functionals (RPBE) where embedded clusters as large as V₂₀O₆₂H₂₄, representing one or two crystal layers of the substrate, are used as models. Results of local binding and charging of differently coordinated surface-oxygen sites as well as densities of states allow a characterization of the detailed electronic structure of the surface. Electronic and geometric details of surface-oxygen vacancies as well as hydrogen adsorption are studied by appropriate clusters. A comparison of the data, concerning vacancy energies, charging, geometric relaxation, and diffusion, shows sizeable variations between different oxygen sites and can give further insight into possible mechanisms of surface relaxation and reconstruction. Hydrogen is found to stabilize at all surface-oxygen sites forming surface-OH and H₂O species. As a result, the binding of surface oxygen with its vanadium neighbors is weakened. Therefore, the presence of hydrogen at the oxide surface facilitates oxygen removal and can contribute to the enhanced yield of oxygenated products near vanadia-based surfaces. Received: 10 April 2000 / Accepted: 25 July 2000 / Published online: 7 March 2001     

The mechanism of oxidation of FeS nanoparticles by molecular oxygen and hydrogen peroxide in dilute aqueous solutions

The kinetic characteristics of the oxidation of iron monosulfide with molecular oxygen and hydrogen peroxide in a neutral aqueous medium were studied. The rate of oxidation of FeS with oxygen was proportional to the concentration of O₂ and quadratically depended on the initial concentration of FeS, W ₀ = k _ef [FeS]²[O₂], where k _ef = (2.5 ± 0.5) × 10⁵ M^?2 s^?1 (pH 8, 22°C). During the oxidation of FeS, the iron ion retained the valence state +2. Oxidation products contained about 50% elemental sulfur. The interaction of FeS with H₂O₂ was characterized by the half-time of reaction less than 15 s. The products of oxidation of initially nontoxic FeS contained toxic compounds, supposedly the sulfoxylate ion HS ₂ ^? .     

Neutron Spectroscopy of the Atomic Dynamics of La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> at Fluorite–Pyrochlore Structural Transformations

The formation of the structural and dynamic properties of La₂Zr₂O₇ in the process of crystallization at the isothermal annealing of initially amorphous precursors obtained by the coprecipitation of corresponding salts has been studied by neutron spectroscopy. The existence of vibrational states characteristic of hydrogen, which is in one or another of the possible chemical states and is incorporated into a solid matrix, has been detected in the spectra of amorphous and fluorite phases. The DFT calculation of the phonon density of states has been performed to analyze the energy structure of experimental phonon spectra for various phases of the La₂Zr₂O₇ compound. The amount of hydrogen in the fluorite phase has been estimated.     

Hydrogen bonding and excited state properties of the photoexcited hydrogen‐bonded (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate complexes

The time‐dependent density functional theory (TDDFT) method has been performed to investigate the excited state and hydrogen bonding dynamics of a series of photoinduced hydrogen‐bonded complexes formed by (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate with water molecules in vacuum. The ground state geometric optimizations and electronic transition energies as well as corresponding oscillator strengths of the low‐lying electronic excited states of the (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate monomer and its hydrogen‐bonded complexes O₁‐H₂O, O₂‐H₂O, and O₁O₂‐(H₂O)₂ were calculated by the density functional theory and TDDFT methods, respectively. It is found that in the excited states S₁ and S₂, the intermolecular hydrogen bond formed with carbonyl oxygen is strengthened and induces an excitation energy redshift, whereas the hydrogen bond formed with phenolate oxygen is weakened and results in an excitation energy blueshift. This can be confirmed based on the excited state geometric optimizations by the TDDFT method. Furthermore, the frontier molecular orbital analysis reveals that the states with the maximum oscillator strength are mainly contributed by the orbital transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital. These states are of locally excited character, and they correspond to single‐bond isomerization while the double bond remains unchanged in vacuum.     

An electron energy loss spectroscopy study of hydrogen physisorption on aluminum and alumina surfaces at room temperature

This paper deals with electron energy loss spectra (EELS) of hydrogen adsorbed at room temperature on Al and Al₂O₃ surfaces. It is shown that while hydrogen physisorption on Al₂O₃ is detected under H₂ pressures in the 10^?4 Torr range, no hydrogen physisorption is observed on clean Al under the same experimental conditions. These observations are consistent with calculations of the potential well depth of interaction between the H₂ molecule and the aluminum and alumina surfaces.     

Theoretical intensities of low frequency recombination lines

The possibility of observable recombination lines below 200 MHz is shown to be greatest for the case of negative absorption in low-density gas in front of strong radio sources. The amplification of background radiation can conceivably exceed 100 per cent, especially when the electron temperature is low; on the other hand if the temperature is sufficiently high, dielectronic recombination may give rise to detectable recombination lines from elements other than hydrogen. The optimum frequencies are in the range 50–200 MHz for the interstellar medium, and 1–100 MHz for such intergalactic matter as may exist. The effects of external radiation fields, thermal and nonthermal, are explored quantitatively and the relevantb _n -factors computed for a 1000-level atom; it is found that even the general galactic radiation field will significantly alter the atomic level populations. Observations of these masing low-frequency recombination lines would be useful in sorting out the hot and cold components of the interstellar medium, and in investigating their properties.     

Effect of iron doping on the hydrophobicity of titanium dioxide film: experiment and simulation

In this study, we carried out experiments and molecular dynamics simulations to identify the effect of Fe doping on the hydrophobicity of a titanium dioxide film. TiO₂ and Fe-doped TiO₂ films were fabricated in situ by atomic layer deposition without annealing. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterise the crystal structure and elemental composition. Iron doping resulted in the TiO₂ becoming more hydrophobic at a macroscopic level, as estimated by atomic force microscopy observations and static contact angle measurements. Furthermore, the effect of iron doping on the structure and kinetics of water molecules on the exterior of TiO₂ were studied by molecular dynamics simulations. On the basis of the XPS results, the Fe-TiO₂ surface matrix has a Ti:Fe ratio of 36:5. In addition, the density distribution of oxygen and hydrogen atoms indicate that interfacial water molecules enter the Fe-TiO₂ film more easily and hydrogen atoms in the water molecules are oriented upward at the interface. The self-diffusion coefficients indicate that iron doping makes the TiO₂ more hydrophobic, which is consistent with the macroscopic test results.