二维和三维氢分子中原子间的电子关联的比较

讨论了非正交基（类氢原子的１ｓ态）和正交基下，二维和三维氢分子的基态波函数中，反映原子间电子关联大小的离子键成分与共价键成分的权重之比η随核间距Ｒ的变化情况，分析了两种基下存在差别的原因，认为正交基下反映的情况更为客观，并得出二维氢分子中原子间的电子关联明显强于三维氢分子中原子间的电子关联这一重要结论。     

含锰钢表面氢原子/氢分子吸附行为的第一性原理研究

采用基于密度泛函理论的第一性原理方法研究了氢原子和氢分子在纯铁表面和锰原子掺杂表面的吸附与解离行为.研究结果表明,氢原子可在纯铁(001)表面稳定吸附,吸附能按照顶位,桥位和心位依次增强;而溶质原子锰降低了氢原子距离表面的位置并强化了氢原子的吸附行为.氢分子在纯铁表面的吸附解离行为取决于氢分子距离模型表面的初始距离和初始空间构型.氢分子平行于纯铁(001)表面时,距离心位1.2?发生解离,而桥位、顶位均不会发生解离;氢分子垂直放置时,距离桥位0.6?、顶位1.0?发生解离,心位不会发生解离.氢分子平行于锰掺杂纯铁(001)表面时,距离桥位0.6?、顶位0.7?、心位1.2?发生解离;氢分子垂直放置时,距离桥位、心位0.8?发生解离,而顶位放置氢分子不发生解离.归纳可知,锰溶质原子掺杂会增加铁基体表面氢原子和氢分子的吸附作用并促进氢分子发生分解.     

螺旋波激发氢等离子体光谱诊断

利用一套螺旋波激发等离子体化学气相沉积（HWP—CVD）发生装置及发射光谱采集装置，原位诊断了不同入射功率、气压、氢气流量下氢等离子体光谱，研究了激发态氢原子的变化情况、氢分子振动温度的变化和激发态氢分子的相对分布。结果表明：     

推动人类文明与进步的物理学 量子理论（三）

化学健是分子中各原子结合成分子的力。1927年，海特勒和伦敦用量子力学理论计算了氢分子中的健能，表明氢刍是由两个氢原子的电子在同一分子轨道中自旋配对（自旋取相反方向）合能量降低而成。     

金属氢研究新进展

简要介绍了金属氢的研究意义和应用前景 ,详细评述了有关的高压实验方法和最近的研究成果及进展 ,特别是固体氢的相图、结构和相变 .近十多年来 ,随着超高压技术的发展 ,已能在金刚石对顶砧 (DAC)上产生30 0GPa的静态压力 ,并可进行高压原位实验研究 .对固体氢进行了高压拉曼、同步辐射X射线、光反射和吸收、同步辐射红外光谱等一系列高压物性和相变研究 .从而确定了固体氢的三个相 ,并提出了可能的相结构 .     

高温高密度条件下氢分子间三体与四体相互作用

 为描述高温高密度条件下氢分子间复杂的多体相互作用，以Ree和Bender对两个氢分子间平均作用势的CI计算结果为基础，提出一种可以描述旋转氢分子外域电子云分布的等效氦原子模型。采用该模型所计算的氢分子三体势与CI计算结果符合较好。还对氢分子间四体势进行了计算。     

光电子离开氢术核的方向

基态氢原子在电磁波的作用下发生电离，这主不是氢原子的光电效应，本文讨论氢原子的电子离开氢核的方向与电磁波的电场强度Ｅ的方向之间的关系。     

固体氢在极端压强下的超导性能

氢元素在常压下具有最简单的晶体结构和物理性质。随着压强增加,氢单质发生相变,由绝缘体转变为金属,被称为金属氢。数值模拟表明,金属氢具有高温超导电性,因此,金属氢研究也被称为高压物理领域的“圣杯”课题。利用基于密度泛函理论的第一性原理计算方法,对固体氢在极端高压(0.5～5.0 TPa)下的结构和超导电性开展了系统研究。研究结果表明：固体氢的高压相变序列为I4₁/amd→oC12→cI16;对于同一种结构,随着压强增加,电声耦合系数减小,费米面处电子态密度减小,特征振动频率增加,超导转变温度发生小幅变化;在2.0 TPa压强下,固体氢的超导转变温度高达418 K(库伦赝势经验值μ^*=0.10)。研究工作将为金属氢及其超导电性的后续理论和实验研究提供参考。     

某些卟啉/醌模型体系中的光诱导氢转移反应机理探索

在质子溶剂中运用光诱导CIDNP与ESR方法直接验证了醌与电子给体间的光诱导氢转移反应分子机理.     

基于氢原子碰撞辐射模型的发射光谱法诊断电子密度

基于碰撞辐射模型,利用氢原子的巴尔末线比对HUST射频负氢离子源等离子体电子密度进行诊断。首先针对HUST离子源等离子体的放电条件,建立了综合考虑氢原子直接激发和氢分子解离激发机制的碰撞辐射模型。基于建立的模型,利用氢原子的巴尔末线比来诊断电子密度。进一步分析了不同的氢原子分子密度比对电子密度诊断的影响,结果表明当电子温度较高,氢分子的解离度较低的等离子体放电状态下,必须同时考虑氢原子直接激发和氢分子解离激发对激发态氢原子的贡献。     

Instability and reconstruction of a thin fluid film under inversion conditions

The development of mechanical instability of a neutral fluid film (liquid helium or hydrogen) under inversion conditions (it does not lie on a solid substrate but hangs from a ceiling) is discussed. Critical parameters of such an instability and the character of surface reconstruction under the action of van der Waals forces, bubble pressure, and gravitational forces are determined. The interrelation with the well-known Frenkel problem of a drop on a solid substrate is pointed out. An electrostatic mechanism is proposed for the stimulation of instability of a thin helium film. This mechanism is promising for the problem of superfluid helium leakage.     

On some hydrogen bond correlations at high pressures

Structural data from in situ high pressure neutron diffractions studies are analysed to show that the measured lengths of O?H and H---O pairs in hydrogen bonds follow the correlation between them established from 0.1 MPa data on different chemical compounds. In particular, the accepted view in literature that the high pressure data on ice VIII differ from it is not supported. For compounds in which the O?H stretching frequencies red shift under pressure, it is shown that wherever structural data is available, they follow the stretching frequency versus H---O (or O---O) distance correlation. For compounds displaying blue shifts with pressure, an analogy appears to exist with ‘improper’ hydrogen bonds. Another pressure effect expected is the symmetrization of a hydrogen bond with evolution of the double-welled, hydrogen bond potential into a single-well potential. Using the results from some recent ab initio electronic structure studies, we show that the bulk modulus shows a discontinuity at this point and this can be taken as signature for hydrogen bond symmetrization. This is supported by analysing a few available experimental data.     

Experimental investigation on the self-ignition of pressurized hydrogen released by the failure of a rupture disk through tubes

Hydrogen is expected to be used as a clean energy carrier. However, when high-pressure hydrogen is suddenly released into the air through tubes, self-ignition can occur by a diffusion ignition mechanism. In this paper, the phenomena of self-ignition and flame propagation during the sudden release of high-pressure hydrogen were investigated experimentally. Experimental results show that self-ignition can occur when bursting pressure is sufficiently high in spite of the shortness of the tube. For example, self-ignition was observed at a bursting pressure as high as 23.5 MPa with 50 mm long tube. When self-ignition successfully occurs, a hydrogen jet flame is produced by the ignition. The flame is then stabilized at the tube outlet. From photodiode signals and flame images, the propagation of a flame inside the tube is confirmed and the flame is detected near the rupture disk as the bursting pressure increases. When the tube length is not long enough to produce self-ignition, a hydrogen flame is observed in the only boundary layer at the end of tube and it quenches after the flame exits the tube. Consequently, the formation of a complete flame across the tube is important to initiate self-ignition, which sustains a diffusion flame after jetting out of the tube into the air. Also, in order to establish a complete flame across the tube, it is necessary to have sufficient length such that the mixing region is generated by multi-dimensional shock–shock interactions.     

Metallization of fluid hydrogen at 140 GPa (1.4Mbar) by shock compression

Abstract

The minimum electrical conductivity of a metal was produced in dense hydrogen using shock compression. Metallization occurs at 140 GPa (1.4 Mbar), 0.6 g/cm³ (ninefold compression of initial liquid-H₂ density), and 3000 K. The relatively modest temperature generated by a reverberating shock wave produced the metallic state in a warm quantum fluid at a lower pressure than expected previously for the crystallographically ordered solid at low temperatures. Future research directions are discussed. Possible scientific and technological uses of metastable solid metallic hydrogen are speculated upon in the unlikely event that the metallic fluid can be quenched to this state at ambient pressure and temperature.     

Hydrolysis acceleration in an Al-Ga-Gr particle material utilizing ultrasound irradiation

The improvement of the hydrogen production rate and the hydrogen conversion ratio is crucial for hydrogen acquirement via Al-water reactions. Present work fabricated an Al-Ga-Gr hydrolyzing particle material, and presents the accelerated hydrolysis by ultrasound irradiation to achieve a high speed of hydrolysis and 100% yield within a short time, and provides a weak coupling model to address the acoustic pressure, velocity and thermal fields in the reactor. The obtained material is characterized with lamellar morphologies comprising AlGa solid solution and Gr. The hydrolysis is accelerated within the cavitation region by peeling off the reaction by-product layer to expose fresh aluminum, and deteriorates after the particle material traversing the cavitation/non-cavitation region boundary. Ultrasound promotes the hydrolysis progress from a diffusion governed mode to a dominated regime of interface reaction without a change to the activation energy.     

多种金属掺杂的镍基催化剂用于中温重整生物油制氢的设计

一种新的由共沉淀法合成的多种金属(铜、镁、铈)掺杂的镍基混合氧化物催化剂,在250～500 oC用于生物油高效重整制氢. 摩尔比为Ni:Cu:Mg:Ce:Al=5.6:1.1:1.9:1.0:9.9的催化剂表现出较高的催化重整活性,在传统的水蒸气重整模式和500 oC条件下,氢产率达82.8%;电催化重整模式中,在400 oC 和3.1 A,氢产率达91.1%.ECR模式中重整温度和通过催化剂电流促进生物油的重整和热裂解.另外催化剂在300～600 oC显示出较高的水煤气变化反应活性,生物油重整过程中催化剂性质的变化利用ICP、XRD、XPS和BET进行了表征. 生物油重整机理基于基元反应、催化剂表征进行了讨论.     

高压下正戊醇的构象和氢键研究

压力是一个重要的物理参量,通过调节物质内部分子、原子间距离和相互作用力,可以引起物质结构和构象变化。正醇是一种最简单的羟基代替烷基链末端氢原子的有机物,通过氢键和烷基链之间的作用力结合在一起,被称为氢键液体。氢键的键能较小,在外部压力作用下,氢键容易被压缩而断裂或网络重排,从而导致晶体结构和对称性的改变,对材料的性能产生重要影响。正戊醇是一种短链正醇,结构虽然简单,却可以作为烷基链结构有机物的典型代表。然而,高压下正戊醇的性质研究较少,尤其压力作用下其构象变化和氢键研究尚未见报道,因此正戊醇高压研究有待进一步深入。拉曼光谱和红外光谱是高压研究中常用的谱学测量技术,能够原位探测压力作用下分子内部基团变化,是研究结构、构象和氢键作用的有效手段。基于此,利用金刚石对顶砧装置(DAC),结合拉曼光谱和红外光谱,在0~12.0 GPa压力范围对正戊醇进行了高压研究。实验结果分三部分讨论:(1)研究了压力作用下正戊醇的结构相变行为。压力在3.2 GPa时,拉曼特征峰变锐变窄,同时有特征峰劈裂和新特征峰出现的现象,说明在该压力点发生一次液固相转变。(2)揭示了正戊醇在高压下的构象变化。正戊醇存在两种构象:反式构象和扭曲构象。通过分析两种构象特征峰随压力的变化,发现正戊醇发生液固相转变的过程伴随有构象变化,液态时以扭曲构象为主,固态时以反式构象为主。(3)探究了高压对正戊醇氢键的影响。羟基的特征峰随压力的增加发生红移,说明在加压过程中氢键作用增强。伴随液固相变,羟基特征峰劈裂成多个峰,形成新的氢键网络或团簇,且随压力的增加氢键网络或团簇逐渐增大,说明氢键对压力非常敏感,且对正戊醇晶体结构的稳定起着促进作用。该研究不仅为正戊醇生产应用提供重要的指导作用,同时为其他同类或复杂分子体系的物理和化学特性研究提供参考。     

Hydrogen adsorption on rhodium: Hydride formed on the surface of thin rhodium films

H₂ interaction with thin Rh films deposited on Pyrex glass under UHV conditions has been studied by simultaneous measurement of work function changes ΔΦ and hydrogen pressure P, at selected constant temperatures: 78 and 298 K. Prior to the adsorption experiments the thin film topography was illustrated using the AFM and STM methods. The influence of hydrogen adsorption on the resistance of thin Rh film was examined in the course of an independent experiment. The number of sites accessible for adsorption on the thin Rh film surface was found determining population of oxygen adatoms within the monolayer at 78 K, when incorporation of these adspecies below the surface is negligible. It was established that at all examined temperatures hydrogen adsorption led to coverage Θ approaching 1 under equilibrium pressure below 10⁻³ Pa, increasing the work function. Under higher H₂ pressure an additional uptake of hydrogen leading to Θ ∼ 1.68 at 298 K, and to Θ ∼ 2 at 78 K is reached. On this surface at low temperatures there exist weakly bound, reversibly adsorbed, positively charged adspecies characteristic for hydrogen adsorption on transition metal hydrides. The change of thin Rh film resistance caused by hydrogen adsorption was not measurable.     

氢在HR－1不锈钢中迁移特性的热动力方法研究

本文研究了氢在ＨＲ－１不锈钢中热动力驱动的宏观迁移特性。用不同的方法（电化学方法和１０５ｐａ氢压强下高温气相法）使试样充氢，然后研究加热升温放气规律，得到了在有意义的温度范围内出气峰的位置以及氢在ＨＲ－１材料中扩散、溶解、渗透系数与温度的关系，并与渗透法测得的结果和国外类似实验结果符合得较好。这些数据对估计未来聚变堆中氚的投料量和氚的渗透漏失有实际意义。