Heusler合金Li2AlX(X=Ga，In)的晶格动力学和电子特性

本文计算了Heusler合金Li₂AlGa和Li₂AlIn的晶格参数、体积模量、体积模量的一阶导数、 电子能带结构、声子色散曲线和声子态密度,并与密度泛函理论中的广义梯度近似计算结果进行比较. 计算的晶格参数与文献有很好的一致性. 两个Heusler合金的电子能带结构表明它们是半金属结构. 并利用声子色散曲线和声子密度图研究Heusler合金晶格动力学. Li₂AlGa和Li₂AlIn Heusler合金在基态呈现动力学稳定.     

UO2的电子结构及光学性质的第一性原理研究

采用局域自旋密度近似 (LSDA)和有效库仑相关能 (U) 方法研究了UO₂的晶格参数、能带结构和光学常数. 计算得到的UO₂晶体的晶格常数为5.40 ?,带隙宽度为1.82 eV,正确预测了UO₂的反铁磁性半导体基态性质. 能带结构和介电函数的分析结果表明,铀的6d电子在晶体场中发生劈裂形成两个能级,与实验结果较为符合.     

第一性原理模拟U在Gd2Zr2O7烧绿石中的固溶

采用第一性原理密度泛函理论模拟U在Gd₂Zr₂O₇烧绿石中的固溶,在低浓度U掺杂时,Gd₂Zr₂O₇烧绿石保持烧绿石结构;随着U掺杂浓度增加,Gd₂(Zr_{2-y}U_y)O₇和(Gd_{2-y}U_y)Zr₂O₇体系的晶格常数发生线性变化．计算结果表明,由于总能较低,U原子更偏向于替代无序换位后Gd₂Zr₂O₇晶格中B位的Gd原子．     

特定位点上CO2与(TiO2)n团簇相互作用的第一性原理研究

本文基于密度泛函理论系统地研究了(TiO₂)_n团簇上二氧化碳(CO₂)的吸附和活化性质. 计算结果表明,CO₂更倾向于吸附在(TiO₂)_n团簇的桥氧原子上,形成“化学吸附”碳酸盐络合物. 而CO更倾向于吸附到末端Ti-O的Ti原子上. 发现计算得到的碳酸盐振动频率值与实验获得的结果非常吻合,这表明配合物中CO₂的几何构型与其线性型相比,有微小的弯转. 通过对电子结构、电荷密度、电离势、HOMO-LUMO以及态密度的分析,证实了CO₂与团簇之间的电荷转移以及相互作用. 从预测的能量分布图来看,(TiO₂)_n团簇上的CO₂活化与结构密切有关,相比于块体的TiO₂,CO₂在团簇结构上更易于吸附和活化.     

压力对纳米CoFe2O4/SiO2复合材料结构的影响

 采用溶胶-凝胶工艺和高温高压实验技术,制备了纳米CoFe₂O₄/SiO₂复合材料。利用X射线衍射仪、扫描电子显微镜和振动样品磁强计,对样品的结构、微观形貌和磁性进行了研究,并对CoFe₂O₄中阳离子的占位情况进行了讨论。结果表明,随着处理压力的升高,样品的晶粒尺寸增大,晶格常数减小,比饱和磁化强度增大。通过计算结果可以推断,压力的升高导致CoFe₂O₄中的部分Fe³⁺从A位移向了B位,而部分Co²⁺则从B位移向了A位。     

BC5力学性质的第一性原理计算

采用平面波赝势密度泛函理论方法对0—60 GPa静水压下BC₅ 六角晶系P3m1和四方晶系I4m2结构的平衡态晶格常数、弹性常数、各向异性以及泊松比与Cauchy扰动进行了研究. 研究结果表明, BC₅的两种结构在高压下是稳定的, 且不可压缩性随着压强的增加而增大. 另外, 对其电子结构也进行了计算, 计算结果表明, BC₅存在一个较宽的带隙, 两种原子间有较强的共价杂化, 材料的性质主要由B的2p¹和C的2p²态电子共同决定. 压强对材料带隙和费米能级附近的态密度几乎没有影响, 只引起微小的漂移, 可推断其很好的高压稳定性.     

使用发射光谱对H2稀释情况下的感应耦合H2/C4F8等离子体中碳氟基团的研究

在射频输入功率为400W，气压为0.8Pa的条件下，使用光强标定的发射光谱方法研究了感应耦合H₂/C₄F₈等离子体中CF, CF₂, H和F基团的相对密度随流量比R=H₂/(H₂+C₄F₈)的变化情况，而HF基团相对密度的变化由四级质谱仪探测得到。结果表明等离子体活性先随着R的增加而升高，然后随着R的进一步增加而下降。在流量比从0逐渐上升到0.625的过程中，CF和CF₂基团的相对密度不断降低。实验中测得的CF基团的相对密度[CF]与理论计算得到的[CF]有很好的一致性说明了电子与CF2基团的碰撞反应是CF基团产生的主要原因。文中还讨论了HF基团。     

Y3Al5O12的热输运性质的第一性原理研究

基于密度泛函微扰理论（DFPT）结合模守恒赝势方法进行晶格动力学模拟.得到了钇铝石榴石（YAG）的声子态密度、分波声子态密度和声子的色散谱.利用第一Brillouin区的特殊点取样方法,计算了YAG的比热容和布局数平均的声子群速度.在非谐相互作用下,利用Fermi黄金公式结合第一Brillouin区的特殊点取样方法,得出了YAG非谐声子平均自由程.综合考虑了两种声子散射机制,得到了YAG陶瓷的热导率.结果表明,对于YAG陶瓷,在低温时,晶界散射将对热阻起主要作用;在高于一定温度时,三声子相互作用对热阻的贡献将占主导地位.同时也从理论上证明了Sato等提出的在室温以上,YAG陶瓷与单晶的热导率的差异可以忽略的观点.所得到的热导率、比热容随温度的变化与实验结果很好地符合.     

第一性原理计算高压下金红石TiO2的结构不稳定性及热学性质

采用第一性原理计算研究了金红石TiO₂结构在高压下的不稳定性及热力学性质. 计算的高压下结构参数和零压的声子色散曲线与实验数据十分吻合. 进一步模拟了在不同压力下的声子曲线,在压力下,声子曲线不断软化,?点附近的振动频率不断减小直至虚频,意味着结构的不稳定,根据计算的不同压力下的弹性常数获得了其力学不稳定性,结果表明金红石结构TiO₂在压力高于17.7 GPa时变得不稳定. 根据准谐近似,获得了金红石TiO₂结构的热力学性质,计算结果与现有     

Au-MgB2-Au纳米结点的负微分电阻效应

运用密度泛函理论结合非平衡格林函数的方法对MgB₂直线原子链与两半无限Au(100)电极构成纳米结点的电子输运特性进行了第一性原理计算．在模拟Au-MgB₂-Au纳米结点的拉伸过程中,计算了结点在不同距离下的结合能与电导．结果发现结点的Au?B键长为1.90 ?,B-Mg键长为2.22 ?时,结合能最大,结构最稳定,此时结点平衡电导为0.51G₀ (G₀=2e²/h)．通过计算投影态密度发现电子通     

Lattice dynamics of MgSiO3 perovskite

A lattice dynamical study of the geophysically important mineral MgSiO₃ in its orthorhombic perovskite phase, with space group Pnma (D _2h ¹⁶ ) has been carried out using a rigid ion model, with the potential consisting of Coulombic and short-ranged interactions. With the help of program DISPR, the ionic charges and radii were optimized using the equilibrium conditions. The resulting potential model is employed to predict the elastic constants and the phonon dispersion relations. The computed long wavelength optic modes are in good agreement with the corresponding experimental Raman and infrared active bands. The phonon density of states has been obtained and is used to evaluate the specific heat, the mean square displacements and thermal parameters of atoms.     

Heat capacity anomaly in UO2 in the vicinity of 1300 K: an improved description based on high resolution X-ray and neutron powder diffraction studies

X-ray and neutron powder diffraction studies of UO₂ were performed under controlled oxygen partial pressure between room temperature and 1673 K. More than 40 neutron diffraction patterns were recorded. The thermal expansion coefficient of UO₂ and the temperature dependence of Debye-Waller factors for oxygen and uranium atoms were determined. The dependence of Debye-Waller factors as a function of temperature is linear and the thermal expansion coefficient follows the classical Debye regime within the temperature range 300-1000 K. Above 1200 K, a departure from this quasi-harmonic behavior is clearly observed. Both an abnormal increase of the thermal expansion and of the oxygen sublattice disorder are evidenced. The departure of the lattice parameter from a linear thermal variation is found to be thermally activated with an effective activation energy close to 1 eV, very similar to the activation energy already found for the electrical conductivity. This new result suggests that polarons may affect the mean lattice parameter. A new thermodynamic model is then proposed to explain the heat capacity thermal variation by only three contributions: harmonic phonons, thermal expansion and polarons.     

Physico-Chemical Characteristics of Uranium Oxide Microspheres Produced by Internal Gelation

The developed Sol-Gel Hydrolysis Process was applied to produce uranium oxide microspheres suitable for use as nuclear fuel. Different preparation conditions of washing, feed solution aging and microsphere soaking were tried to produce dense UO₃- and UO₂-micospheres. The effect of reduction time and temperature on the density and porosity of the microspheres was carried out to optimize the preparation parameters. The total surface area, total pore volume and pore radius of UO₃- and UO₂-microspheres were measured through N₂ gas adsorption and application of the BET-equation at 77 K. The effect of the preparation conditions on crystallite size of the samples was made through ray diffraction analysis. Examination of the prepared uranium oxides by differential thermal analysis and thermal gravimetric analysis was carried out.     

Self-diffusion of oxygen in superstoichiomertric uranium dioxide in the range of the superion phase transition

The self-diffusion of oxygen in the superion transition range (1300–3000 K) of superstoichiometric uranium dioxide UO_{2 + x} is studied by the method of molecular dynamics using the pair interaction potential recovered from data for the thermal expansion of the UO₂ lattice. It is shown that three portions can be distinguished in the temperature dependence of the coefficient of oxygen self-diffusion in UO_{2 + x} , lnD = f(1/T), for all the compositions studied (x = 0, 0.008, and 0.030). These portions, each being described by the Arrhenius relationship, correspond to the crystalline, transition, and superion states of UO_{2 + x} . At low temperatures (1300–1820 K), the activation energies of oxygen diffusion for the above compositions are, respectively, 2.66 ± 0.44, 1.33 ± 0.10, and 1.00 ± 0.09 eV. At the beginning of the transition region, these activation energies rise to 3.40 ± 0.11, 2.24 ± 0.10, and 1.66 ± 0.60 eV. In the superion state, the activation energy of oxygen diffusion for all the compositions is the same, 1.25 ± 0.15 eV, within the error limit. As the oxygen content in UO_{2 + x} grows, the phase transition temperature decreases considerably and may reach 1600 K at x = 0.2. Comparison with experimental data for the low-temperature oxygen diffusion coefficient and with the data of UO₂ simulation using graphic processors shows good agreement of the results. By comparing the concentration dependences of the oxygen diffusion coefficient that are obtained by magnetic dynamics simulation with experimental data, it is shown that quantitative calculation of these dependences in the case of UO_{2 + x} can be carried out only for compositions with x < 0.03 if the given type of potential is used.     

First-order transition in a 2D classical XY-model using microcanonical Monte Carlo simulations

We have simulated two-dimensional classical XY-model in a microcanonical ensemble using the Monte Carlo technique. Simulations were carried out on a square lattice having 25, 100 or 900-spins with periodic boundary conditions. The nearest neighbour interaction potential was taken to beV(θ)=2J[1−cos¹⁰⁰(θ/2)]. The system energy, mean square magnetization and vortex-density were calculated as functions of temperature. A sudden change in the system energy, vortex density and mean square magnetization was observed at the first-order transition which is associated with this choice of the nearest neighbour interaction potential. The transition temperature increases with decrease in the system size. It is found that the creation of a vortex-antivortex pair costs more energy during the first-order transition than the energy associated with a tightly bound vortex-antivortex pair.     

密度泛函理论研究高温高压下UO2弹性与热力学性能

采用第一性原理与准谐德拜模型研究UO2在高温高压条件下的弹性与热力学性能。UO2在高温高压下仍属离子型晶体,并且弹性性能计算表明,四角方向剪切常数在高温与高压下均保持稳定。高温下弹性常数C44没有明显变化,而高压下C44迅速增大。体积模量、剪切模量与杨氏模量均随压强增加而增大;高温条件下,体积模量、剪切模量与杨氏模量也未出现明显的降低,表明UO2在高温度高压下均可保持良好的力学性能。不同压强下,UO2定容热容均随温度迅速增大,并在1000 K 附近趋近于杜隆-佩蒂特极限。德拜温度则随温度降低,随压强升高。在低于室温条件下,热膨胀系数随温度急剧增加;温度继续增加,系数的增加趋势则逐渐变缓。计算结果还表明,UO2的热膨胀系数在相同条件下,远小于其他核材料。     

A study of thermal parameters of Ag50Pd50 alloy using X-ray diffraction

Thermal parameters of Ag₅₀Pd₅₀ alloy were studied using the in-situ X-ray diffraction (XRD) technique. Diffraction experiments in the temperature range 308-1178 K showed that the alloy forms a face centered cubic (fcc; A1-type) structure. Temperature dependence of the lattice parameter was investigated using the Bragg line displacement method. Results show that the lattice parameter for the alloy increases with increase in temperature. The temperature dependent XRD data was utilized to determine the mean linear thermal expansion (MLTE (%)) and coefficient of thermal expansion (CTE) ‘α’ in the mentioned temperature range. It was observed that the values of CTE vary between 9.3 and 14.6 [K⁻¹][10⁻⁶]. The same data was also utilized to determine the Debye temperatures Θ_D and mean square amplitude of vibration (MSAV) (u²(T)) for this alloy. Values of thermal parameters as determined in this investigation are in good agreement with the estimated values as well as with those for other alloys of noble metals.     

Magnetic interaction in Tm3Fe5O12 studied by means of169Tm and57Fe Mössbauer spectroscopy

The temperature dependence of the hyperfine parameters of thulium iron garnet (Tm₃Fe₅O₁₂) powder was studied from 90 to 550 K using¹⁶⁹Tm and⁵⁷Fe Mössbauer spectroscopy (MB). The spectra were analyzed by least mean square fits to the transmission function. The temperature dependence of the magnetic fields of the thulium nuclei is well described by the mean field model. The coupling constants between the magnetic lattice occupied by the thulium atoms and the magnetic lattices occupied by the iron atoms were derived.     

Ion-scattering structure studies of UO2 surfaces

Planar (111) and stepped (553) surfaces of single crystalline UO₂ have been studied by low-energy He⁺ ion scattering spectroscopy, (ISS). Angular dependent ISS and comparison data from oxide-coated, polycrystalline U indicate that the outermost layer of UO₂(111) is oxygen occupying, to a first approximation, the lattice position expected from a simple termination of bulk structure. A similar study of UO₂(553) indicates that ledge U is covered with excess oxygen.