MgH2(110)表面Pd单原子催化氢脱附反应的第一性原理研究

本文采用第一性原理密度泛函理论计算研究了MgH₂(110)表面吸附单原子Pd后的氢脱附反应. 计算发现,在吸附一个Pd单原子后,MgH₂(110)表面氢脱附反应的能垒可以从1.802 eV显著地降低到1.154 eV,表明Pd单原子对于氢脱附具有很强的催化效应. 并且,Pd单原子催化还可以将氢脱附的温度从573 K显著地降低到了367 K,从而使MgH₂(110)表面的氢脱附反应更加容易和快速地发生. 此外,通过MgH₂(110)表面氢溢出机制的反向过程来讨论了氢脱附反应的微观过程. 该研究表明Pd/MgH₂薄膜在未来的实验中可作为良好的储氢材料.     

Ag4超原子在超原子分子中的SP3杂化特性

为了研究和原子类似的超原子也能用来组建分子和材料的这一特性,以正四面体的Ag₄团簇为例构建了一系列的超原子分子Ag₄X₄(X=H,Li,Na,K,Cu,Ag,Au以及F,Cl,Br)． 基于超级价键模型,可以将正四面体的Ag₄团簇视为4电子的超原子,通过比较Ag₄和C组成的代表分子Ag₄X₄(X=Au,Cl)和CX₄(X=H,Cl)的成键模式和分子轨道,可以发现Ag₄超原子与sp³杂化的C原子相似．能量计算显示超原子分子是稳定的,大能隙和高芳香性也进一步证实了它们的稳定性．     

第一性原理研究LuAlO3中掺杂Ce3+的4f-5d跃迁性质

通过对基态4f电子采用杂化密度泛函理论方法、对5d激发态采用限制性布居方法,研究了LuAlO₃:Ce³⁺体系4f-5d跃迁的相关性质．结果表明,伴随着4f到5d的跃迁,Ce³⁺与8个最近邻配位O原子的平均键长缩短了0.05 ?,而且Stokes位移计算值与实验值相当吻合．在优化计算得到的LuAlO₃:Ce³⁺体系4f基态局域构型基础上,采用角重叠模型计算了5d能级的晶场分裂,与实验结果吻合较好.     

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     

Ag60纳米颗粒[{Cl@Ag12}@Ag48(dppm)12]的结构(其中dppm=双(二苯基膦基)甲烷

本文合成一种新的双膦连接Ag₆₀纳米团簇[{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂],并通过X射线晶体学进行表征. 二十面体的银处于核心位置,里面是中心氯化物组成,外面有48 个银原子/离子的包裹,顶端是12个双(二苯基膦基)甲烷(dppm)配体. 同时利用密度泛函理论对阳离子[{Cl@Ag₁₂}@Ag₄₈(dppm)₁₂]⁺进行计算,以确定该结构是否对应于核心数n=58的超原子. DFT计算的优化结构与X射线一致,但是HOMO-LUMO的能差并不能保证其超级稳定性.     

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。     

Structural and Electronic Properties of Li2Mg(NH)2 for Hydrogen Storage: First-principles Study

应用第一原理方法研究了储氢材料α-Li₂Mg(NH)₂和β-Li₂Mg(NH)₂两种构型的结构性质和电子性质．计算优化得到的晶胞参数和N-H键长符合实验得到的数据．通过Murnaghan状态方程得到了体积模量和零压力下的能量,计算结果表明α-Li₂Mg(NH)₂为基态构型．通过Mulliken布居分析说明α构型的N-Li/Mg的离子特性和N-H间的交互作用都弱于β构型．态密度分析结果表明,价带轨道主要由N原子的s轨道和p轨道占据,并与H原子的s轨道杂化．     

Density Functional Study on Structures and Relative Stability of Gd(H2O)n3+(n=8,9)

用密度泛函理论方法研究了气相和水溶液中Gd(H₂O)_n³⁺(n=8,9)化合物的结构和相对稳定性,其中水溶剂效应利用极化连续介质方法结合多种溶质空腔模型进行模拟．气相计算得到的化合物结构与实验观察结果一致．计算结果表明,在气相中9配位Gd(H₂O)₉³⁺比8配位Gd(H²O)₈³⁺稳定,而在水溶液中稳定顺序刚好相反,这一结果不依赖于计算中采用的空腔模型种类,而且也与实验结果吻合．最后,通过采用各种空腔模型计算Gd³⁺的水合自由能,并与实验值比较,发现当化合物只包含第一层配位水分子时,UA0、UAHF及UAKS空腔模型最适合研究Gd³⁺在水溶液中的性质．     

M@C28(M=Ti,Zr,Hf)内裹配合物的电子结构及其稳定性

用B3-LYP赝势模型的密度泛函理论,对M@C₂₈(M=Ti,Zr,Hf)内裹配合物电子结构进行从头计算研究.计算包括确定稳定的几何结构参量的分子几何结构进行优化和自然键轨道分析.结果发现Ti与C₂₈基团的相互作用明显不同于Zr(Hf)与C₂₈的相互作用,表现在原子的电子组态、成键特征和电子态分布等诸多方面.另外,结合能估算表明,这三种内裹配合物均能稳定存在,但Zr@C₂₈和Hf@C₂₈比Ti@C     

α-Al2O3(0001)表面原子缺陷对ZnO吸附影响

采用基于密度泛函理论的分子动力学方法，对α-Al₂O₃(0001)表面 Al，O原子空位缺陷及其对ZnO吸附进行了理论计算.电子局域函数显示了表面空位处的电子密度变化，表面Al原子空缺处有非常明显的缺电子区域，悬挂键临近O的电子密度增大，有利于对Zn的吸附；O原子空缺处的Al原子处存在孤立电子，其ELF值为005—03，将有利于同电负性较大的O或O^2-结合.通过吸附动力学模拟与体系能量的计算发现，表面缺陷显著增强了表面 的化学吸附，空缺原子处都被吸附原子填补，吸附结合能远大于单晶表面的情况.在Al空缺的表面，由于ZnO的O与表面O形成双键，破坏了α-Al₂O₃(0001)表面O六 角对称结构，减小了 O的表面扩散，从而不利于规则的ZnO薄膜生长.相反，O的空缺表面，弥补了α-Al_{2O3(0001)表面O空位缺陷，不影响基片表面O六角对称结构.}     

Bestimmung der absoluten Übergangswahrscheinlichkeit der Linie C II 2511 Å

The transition probability of the CII line 2511 Å has been determined from relative intensity measurements of singly ionized carbon lines calibrated by the life time value of the 4² F ⁰-level obtained by the beam-foil method. The spectra were exposed from a quasistationary pulsed discharge between carbon electrodes in a helium-hydrogen mixture. Assuming LTE Saha's equation for C III/C II yielded the plasma temperature while the electron density was determined from theH _β profile. The transition probability of the line CII 1 324 Å was evaluated by the aid of the well-known life time of the² D ⁰-level.     

Interaction of frequency modulated light pulses with rubidium atoms in a magneto-optical trap

The spatial displacement of the ⁸⁵Rb atoms in a Magneto-Optical Trap (MOT) under the influence of series of frequency modulated light pulse pairs propagating opposite to each other is measured as a function of the time elapsed after the start of the pulse train, and compared with the results of simulations. Adiabatic excitation and consecutive de-excitation take place between the ground 5²S_1/2 (F=3) and the 5²P_3/2 (F'=2, 3, 4) excited levels as the result of the interaction. The displacement of the ⁸⁵Rb atoms is calculated as the solution of simple equation of motion where the expelling force is that arising from the action of the frequency modulated light pulses. The restoring and friction forces of the MOT are taken into account also. The system of Bloch equations for the density matrix elements is solved numerically for transitions between six working hyperfine levels of the atom interacting with the sequence of the frequency modulated laser pulses. According to these simulations, the momentum transferred by one pulse pair is always smaller than the expected 2ħk, (1) where ħ is the Plank constant and k=2π/λ where λ is the wavelength, (2) having a maximum value in a restricted region of variation of the laser pulse peak intensity and the chirp.     

Coherent control in a single semiconductor quantum dot exhibiting excitonic and biexcitonic features

We have developed a simplified theoretical model to analyze the phenomenon of coherent control in a single semiconductor quantum dot excited by a pair of optical pulses. The first pulse populates a biexciton state by two-photon absorption while the second pulse generates population in the exciton state via deexcitation from the biexciton state. We have used density-matrix analysis for a 3-level system to calculate the time dependent biexciton and exciton state populations. The usual 9×9 matrix has been reduced to a 6×6 matrix. The time variation of the population in each state and it’s dependence on the pulse delay manifest coherent control. Numerical estimates made for In_0.5Ga_0.5As/GaAs single quantum dots qualitatively agree with the recent experimental results. PACS 78.67.Hc; 42.50.Md; 78.55.Cr     

Photoinduced semiconductor-metal phase transition in a peierls system

The dynamical equation for the order parameter of the metal-semiconductor phase transition, as well as the kinetic equation for the density of nonequilibrium electron-hole pairs of a Peierls system in a light field, has been derived. An expression for the time τ of the nonthermal photoinduced semiconductor-metal phase transition has been obtained from these equations for the case of an ultrashort light pulse. It has been shown that, to initiate the phase transition, the energy density W of the light pulse must be higher than the critical value W _c. The W _c, τ, and optical absorption coefficient γ₀ that are calculated in the framework of the proposed model are in agreement with the experimental data (W _c ≈ 12 mJ/cm², τ ≈ 75 fs, and γ₀ ≈ 10⁵ cm^?1) on the irradiation of a vanadium dioxide film by a laser pulse with a duration of τ_p ≈ 15 fs, a photon energy of ?θ₀ = 1.6 eV, and an energy density of W = 50 mJ/cm².     

基于光放大的长脉冲抽运太赫兹激光

为了获得较窄增益带宽、较大光强的太赫兹辐射,尝试了利用TEA CO₂激光器对6 W可调谐连续波CO₂种子激光实行双程光放大实验,以期望获得长脉冲、高峰值功率的抽运光.通过实验,获得了大约30倍的放大系数,放大光输出功率随种子光注入功率的增加而增加,其中10 P （20）支线表现更加突出,并且被放大的激光支线半峰全宽在14 μs左右.基于这种长脉冲抽运源,建立了一种产生脉冲太赫兹的动力学模型,给出了产生太赫兹辐射的饱和抽运光强表达式,确定了抽运光的光强范围.另外, 关键词： 激光物理 长脉冲 动力学模型 太赫兹激光     

光泵重水气体产生THz激光的半经典理论分析

从半经典密度矩阵理论出发，采用三能级系统模型对光泵重水气体产生太赫兹激光进行了理论分析，求解得到了脉冲光泵重水气体分子产生太赫兹激光过程中激光信号增益系数G_s和抽运光信号被吸收系数G_p的表达式，通过迭代法对太赫兹激光信号的输出光强进行了数值计算，理论计算得到的频谱特性曲线完全符合受激Raman辐射的频谱特性，即频谱宽度较大、输出光强随抽运失谐量的改变而变化明显等特征.在脉冲激光抽运受激Raman辐射过程中，工作介质D₂O气体分子的偶极矩由于受到抽运脉冲光场的扰动发生变化，在频谱特性曲线中表现为受激辐射THz信号的谱线发生了分裂.理论计算结果与已报道的实验结果能较好地相符.     

铯原子里德堡态Stark能量及电偶极矩的测量和理论计算

里德堡原子由于具有体积大、寿命长、易极化及在外电场中能级易于操控等特点, 已经成为了目前物理学领域研究的热点之一. 本文在磁光阱中实验测量了铯原子15P_3/2和16P_3/2态的Stark光谱,根据光谱给出了15P_3/2和16P_3/2|m|=1/2 Stark态在0-1400 V/cm场强范围适用的Stark 能量和偶极矩的经验性解析表达式; 用数值方法求解薛定谔方程获得了这些态的Stark能量、偶极矩和电子几率密度分布. 电子几率密度分布定性说明了计算的偶极矩矢量的方向是正确的. 计算的Stark能量、偶极矩与实验结果相一致.     

Scattering of ultrashort laser pulses on “ion‐sphere” in dense plasmas

Scattering of ultrashort electromagnetic pulses on the dense strongly coupled plasma is under consideration in the frame of hard ion sphere model. The electron distribution inside the ion sphere is obtained from self‐consistent solution of the Shrodinger equation for bound electrons and the Poisson equation for free electrons. The electron density distribution is determined by plasma electron temperatures. The ion density of Al plasmas under consideration is of the order of 10²⁰–10²² cm^?3, the electron temperature changes between 54 and 816 eV. Dynamical polarizability of the hard sphere determining the scattering cross sections is calculated using the modified local plasma frequency approximation. The spectrum of scattering cross section has maxima in the vicinity of the mean plasma frequency. Dependencies of scattering probability on carrier frequency and pulse duration are analysed in detail. The transition of the total scattering probabilities from nonlinear time dependence at small times to standard linear ones with the increase of pulse duration is demonstrated.     

Electromagnetically induced transparency in a cascade-type quantum well subband system under intense picosecond excitation

The coherent light–matter interaction in a 4-level cascade-type subband system of an asymmetric GaAs/AlGaAs quantum well structure is studied in pump-probe transmission experiments with picosecond (ps) time resolution. Coupling two excited subbands by an intense mid-infrared laser pulse at low sample temperatures is found to result in a substantially increased transparency of the fundamental e₁–e₂ transition. We find a reduction of the absorption coefficient by ~80%, which is one of the most pronounced electromagnetically induced transparency in solid state systems observed so far.