氢化钚与空气反应的热力学平衡计算

氢化钚与空气系统中有6个独立组分,即PuH2.7(s)、PuN(s )、Pu2O3(s)、N2(g)、O2(g)和H2(g)及4个元素,故有2 个独立反应。这两个反应的ΔG°<<0,计算表明：气相和固相质量衡算基本趋于平衡 ,与文献［6］实验结果相符。因而,氢化钚与空气反应极快。这对于钚材料的贮存有一定 参考意义。     

二氢化钚分子激发态结构的外场效应

采用密度泛函(DFT)方法B3LYP/Gen，在Pu为SDD基组、H为6-311++G^**基组水平上优化得到了分子轴方向不同电偶极场(-0.005—0.005a.u.)作用下，二氢化钚的基态电子状态、几何结构、电偶极矩和分子总能量.在优化构型下用同样的基组采用含时密度泛函(TDDFT)方法(TD-B3LYP)研究了同样外电场条件下对二氢化钚的激发能和振子强度的影响.计算结果表明，分子几何构型与电场大小和方向呈现较强的依赖，电场强度增加基态偶极矩随电场强度线性增加，H-Pu-H的角度线性减小，分子总能量线性减小；激发能随电场强度增加而减小，且对电场方向的依赖呈现近似对称性，满足Grozema关系.电场对振子强度的影响比较复杂，但仍满足跃迁选择定则. 关键词： 二氢化钚 激发态 电偶极场 TD-DFT     

钚氧化物中氢行为的第一性原理研究

通过第一性原理计算和原子级热力学方法,系统研究H、H₂在PuO₂和α-Pu₂O₃中的吸附、扩散和溶解行为.研究发现：氢的上述行为均是吸热过程,但在α-Pu₂O₃与PuO₂中有显著不同：在α-Pu₂O₃中H可自发聚合成H₂,但在PuO₂中H难再聚合;在α-Pu₂O₃中H、H₂均能扩散,通常H会聚合成H₂再扩散,在PuO₂中H₂解离后才能扩散,且PuO₂中H沿高势能面的扩散比α-Pu₂O₃中H₂扩散更容易;在氢压、温度驱动下,氢在α-Pu₂O₃中存在H₂溶解到H+H₂混合溶解机制的转变,平衡气压P_H2远小于H在PuO₂中溶解的情况.基于此,给出PuO₂和α-Pu₂O₃中氢行为的微观图像和PuO₂的阻氢微观机制：PuO₂表面限制H₂解离、渗透,PuO₂块体限制H的溶解,但不阻止H扩散.结合钚氧化层表面氢行为研究获得了钚氢化孕育期的微观机制,为孕育期全过程理论建模提供依据.     

气固氢化反应热力学函数计算的近似方法

在有效原子实势近似下, 采用Gaussian 98程序及B3LYP/SDD密度泛函方法计算得到了ZrCo和ZrCoH分子的结构及能量E、熵S. 在此基础上, 近似以气态分子总能量中的振动能Ev代替该分子处于固态时的振动能量, 以电子运动和振动运动熵Sev代替分子处于固态的熵, 计算了不同温度下固态ZrCo与H2, D2, T2反应的热力学函数ΔH, ΔG, ΔS及氢化反应平衡压力, 导出了氢化反应温度与平衡压力的依赖关系. 计算得出ZrCoH, ZrCoD, ZrCoT的生成焓(398-598 K)分别为82.81 , 81.54和80.49kJ/mol, 与实验结果很好符合.     

氢化物发生-电感耦合等离子体原子发射光谱法同时测定人发中氢化元素和非氢化元素

采用连续氢化物发生法,在酸性介质中,对人发样品中可形成氢化物的元素（As,Se,Pb,Hg,Sb)和棵氢化元素（Zn,Cr,Mg,Mn,Ca,Fe,Cu,Ni,Cd,Al,Co,Mo,Ba)进行同时测定。研究了酸度、NaBH4的浓度、载气流速、清洗时间对氢化元素的影响,比较了传统雾法和（雾化＋氢化法）对氢化元素和非氢化元素的影响,选择了最佳分析条件。对标准人发样品中的18种元素进行了测定,结果令人满意。     

化学自催化混沌反应模型中的耦合作用与混沌同步

选用混沌自催化反应作为子系统 ,构造了耦合自催化反应系统 ,研究了耦合变量、耦合系数对混沌动力学行为的影响 ,给出了不同耦合系数下系统的动力学特征 ,探讨了耦合作用机制 .结果表明 ,耦合作用能明显地改变子系统的动力学行为 ,强化系统间的相关性 .耦合后的混沌运动受到调整与抑制 ,耦合强度加大时 ,呈现出混沌运动轨线的周期化 ,耦合系数大于临界值 ,两子系统实现了完全的同步 .不同变量的耦合时 ,影响最大的是第二种变量 .对于三种物质均有耦合时 ,更容易出现混沌的抑制、运动状态的锁相与周期化和混沌的完全同步 .     

二氧化钚分子激发态结构的外场效应

在相对论有效原子实势近似下,用B3LYP密度泛函方法计算优化得到分子轴方向不同电偶极场(-0.005~0.005 a.u.)作用下,二氧化钚的基态几何结构、电偶极矩和分子总能量.在优化构型下,用同样的基组,采用含时密度泛函(TDDFT)方法(TD-B3LYP),研究同样外电场条件下,对二氧化钚的激发能的影响.计算结果表明,在外场作用下,对PuO₂的前5个激发态电子跃迁光谱属于可见-红外-远红外光谱,波长为501.47~10291.5 nm,这是钚原子的奇异特征;激发能与外电场的关系近似满足Grozema等人提出的关系.     

CO氧化反应耦合下SrFe1.125Co0.375Oy的氧渗透行为

报道ＳｒＦｅ１．１２５Ｃｏ０．３７５Ｏｙ致密陶瓷膜在高氧梯度下的氧渗透行为。将膜的一端置于空气中,另一端引入ＣＯ,通过ＣＯ的氧化反应降低氧分压,增大膜两端的氧分压梯度。研究发现：９００℃时氧渗透率高达１６．０＊１０＊－７ｍｏｌ／ｃｍ＾２ｓ。在８５０℃以上,氧渗透率与温度的依赖关系不显著,而氧渗透量与ＣＯ分压成线形关系,并且与膜的厚变化基本无关,这表明在该膜材料的渗透过程是受表面反应控制的。     

PuH2分子激发态的外场效应

采用密度泛函(DFT)方法B3LYP/Gen,在Pu为SDD基组、H为6-311 G**基组水平上优化得到了分子轴方向不同电偶极场(-0.005~0.005 a.u.)作用下,二氢化钚的基态电子状态、几何结构和分子总能量.在优化构型下用同样的基组采用含时密度泛函(TDDFT)方法(TD-B3LYP)研究了同样外电场条件下对二氢化钚的激发能、振子强度、自旋污染和Pu原子正电荷的影响.计算结果表明,分子几何构型与电场大小和方向呈现较强的依赖,H-Pu-H的角度线性减少,分子总能量线性减少;自旋污染随电场增加线性增加;Pu原子正电荷随电场增加而线性减小;激发能随电场强度增加而减小,且对电场方向的依赖呈现近似对称性,满足Grozema关系.电场对振子强度的影响比较复杂,但仍满足跃迁选择定则.     

在极化转移NMR实验中的质子同核耦合调制效应

本文以INEPT脉冲序列为例,从理论和实验上研究了在极化转移NMR实验中的质子同核耦合调制效应,并对与具有1/2自旋的被观测核之间有不同耦合常数的两组质子同时进行极化转移的情况作了探讨.     

Equilibrium composition for the reaction of plutonium hydride with air

There are six independent constituents with 4 chemical elements, i.e. PuH2.7(s), PuN(s), Pu2O3(s), N2, O2 and H2, therefore , the system described involves of 2 independent reactions ,both those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.     

不同形状孔缝微波耦合的实验研究

 探讨了椭圆、圆环、方环、十字交叉形、圆形、正方形、正三角形及双矩形孔缝在2～18GHz频率范围内的耦合系数，并与矩形孔缝的耦合特性进行了比较。结果表明: 各种不同形状孔缝微波耦合的共振特性与其纵横比有关, 纵横比较大的孔缝耦合共振现象比较明显，纵横比较小的孔缝耦合特性趋于高通；各种孔缝的共振频率与孔缝长度有密切关系。     

The MD simulation of thermal properties of plutonium dioxide

The thermodynamic properties of PuO₂ have been investigated between 300 and 3000 K by molecular dynamics (MD) simulation with empirical interaction potential. The properties include melting point, lattice parameter variation, enthalpy and heat capacity. The melting point of two-phase simulation (TPS) is in agreement with the experimental value, and it gives a much lower value than one-phase simulation (OPS). The lattice parameter and heat capacity at high temperatures are expressed as a(T)=5.38178+4.38×10⁻⁵T+6.5525×10⁻⁹T²+0.9362×10⁻¹²T³$a(\mathrm{T})=5.38178+4.38\times 10^{-5}T+6.5525\times 10^{-9}{T}^2+0.9362\times 10^{-12}{T}^3$ and C_P(KJ⋅mol⁻¹⋅K⁻¹)=18648.8e^474.5/T/(T²(e^474.5/T−1)²)+9.337×10⁻⁶T$C_P(\mathrm{KJ}\cdot {\mathrm{mol}}^{-1}\cdot {\mathrm{K}}^{-1})=18648.8e^{474.5/T}/(T^2{(e^{474.5/T}-1)}^2)+9.337\times {10}^{-6}T$, respectively. True linear thermal expansion coefficient (TLTEC) α is about 8.89×10⁻⁶ K⁻¹ at 300 K. Our simulation results are in good agreement with experimental and other theoretical data.     

矩形孔缝耦合特性实验研究

 对矩形孔缝在微波频率为2～18GHz范围内的耦合系数进行了实验研究；建立了实验方法和实验装置。实验结果表明：对于矩形孔缝，当入射电场方向垂直于孔缝长边时，在微波波长约等于2倍孔缝长度时，发生共振效应，在该频率附近一定带宽内耦合系数最大，并且在共振频率处存在着场增强效应。     

The electronic transport properties for a single-wall ZnO nanotube with different coupling interfaces

The transport properties of a single-wall ZnO nanotube contacted with two Au (Al or Cu ) electrodes are investigated by a theoretical approach. Our results suggest the contact resistance for ZnO nanotube connected with Au electrodes is the largest one as compared with Al and Cu acting as electrodes. The local density of states (LDOS) near the ZnO nanotube/Cu(Al) interface shows the strong electronic interaction. Also shown is that for Au–ZnO system, we can observe a best rectifying performance, the next is the Al–ZnO system, and the third is Cu–ZnO system. This rectification is also fully rationalized by the calculated transmission spectra, the spatial distribution of the lowest unoccupied molecular orbital and highest occupied molecular orbital states, and the electrostatic potential distribution.     

Characterization of coupling power for single-mode fiber fusion

Fabrication of single-mode fiber coupler by heating fibers on a flame is very common and popular. However, controlling the input and the output power quantities of the fiber coupling process is neither easy nor similar. Power losses occur at the coupling length as the effect of the geometry and structure of fibers during and after fusion. In application, the power losses will affect sensor devices, e.g. optical switch. This paper proposes power splitting into the second fiber junction as a new model by deriving and integrating the coupling power with two conditions of refractive index changes. First is the change in the vertical part and second is the change in the vertical and the horizontal parts. Both conditions are studied by perpendicular and parallel directions of coupling power. The model is examined with a linear change of refractive index where power absorption and reflection are accumulated by power losses. The result shows that power increases as the effect of losses by simulation. These power losses are lost by radiation out of cladding and fiber heating.     

The electronic spectrum of tantalum hydride and deuteride

The diatomic molecule tantalum hydride (TaH) and its isotopologue tantalum deuteride (TaD) have been detected for the first time by laser excitation spectroscopy. The gas-phase molecules were produced in a hollow cathode discharge. Two red-degraded bands, one arising from TaH at 636 nm and the other from TaD at 635 nm, have been recorded at sub-Doppler resolution by intermodulated fluorescence spectroscopy. A rotational analysis shows that both bands are Ω = 2←2 in character, with well-resolved Ω-doubling in the upper state of TaH. Analysis of the ¹⁸¹Ta magnetic dipole and electric quadrupole hyperfine structure reveals that the lower X³Φ₂ electronic state of the two transitions arises from a σ²πδ electronic configuration, in agreement with previous theoretical calculations. The bond length in the TaH X³Φ₂ (v = 0) level is found to be 1.756960(4) Å.     

高功率微波缝隙耦合效应的试验研究

 利用高功率微波源对预设的11种不同尺寸的缝隙做了耦合效应试验，得到了这11种缝隙对试验波段的一般耦合特性。试验结果表明：窄缝的耦合效应有较强的极化特性；从波长与缝隙的长度相对关系对耦合效应的影响来看，波长与缝隙的长度相当时耦合效应最强；在UWB，L，S，X几个波段内，缝隙的宽度越窄，耦合效应越弱；缝隙的深度能明显影响其耦合效应，随缝深的增加，耦合效应逐渐减弱；辐射波脉宽变化对耦合效应基本没有影响。     

微波孔缝线性耦合函数研究

 讨论了微波脉冲通过孔缝线性耦合进入腔体内的研究方法。给出了线性耦合的物理基础,定义了耦合函数，并导出了耦合函数随入射电场极化方向变化的公式。简要描述了数值求解孔缝线性耦合的时域有限差分方法以及修正算法。给出了以矢量网络分析仪HP8510C为主要设备测量耦合函数的实验方法。通过耦合函数的研究，观察到了共振效应和增强效应等现象，给出了微波孔缝耦合发生共振的普适公式。分析了测量探头对耦合函数测量的影响，验证了耦合函数随入射电场方向变化的公式。理论、数值和实验结果符合得较好。