Theoretical study of stereodynamics for the D'+DS(ν = 0,j = 0)→D'D+S abstraction reaction

Quasiclassical trajectory (QCT) calculations have been performed for the abstraction reaction, D' +DS(v = 0, j = 0)→D'D+S on a new LZHH potential energy surface (PES) of the adiabatic 3A' electronic state [Lü et al. 2012 J. Chem. Phys. 136 094308]. The collision energy effect on the integral cross section and product polarization are studied over a wide collision energy range from 0.1 to 2.0 eV. The cross sections calculated by the QCT procedure are in good accordance with previous quantum wave packet results. The three angular distribution functions, P(θ_r), P(φ_r), and P(θ_r,φ_r), together with the four commonly used polarization-dependent differential cross sections ((2π/σ)(ds₀₀/dω_t), (2π/σ)(ds₂₀/dω_t), (2π/σ)(ds₂₂₊/dω_t), (2π/σ)(ds_21-/dω_t)) are obtained to gain insight into the chemical stereodynamics of the title reaction. Influences of the collision energy on the product polarization are exhibited and discussed.     

双色场诱导气体产生相干可控的四次谐波

利用钛宝石飞秒激光器输出的基频脉冲ω及其倍频脉冲2ω所构成双色场作用空气, 实验中检测到了中心波长处于真空紫外波段的四阶谐波. 在气体未发生电离的情况下, 四次谐波强度对双色场的能力依赖关系显示其产生是参量过程2ω+ω+ω→4ω的贡献. 当气体发生电离, 四次谐波强度与双色场相对相位有关, 可通过双色场相干控制. 实验研究了四次谐波对双色场相位的依赖性以及与太赫兹波的关联性, 其结果与数值模拟结果相符, 分析发现当气体发生电离时四次谐波的产生过程存在太赫兹辐射Ω_THz的参与, 是参量过程2ω+2ω±Ω_THz→4ω和2ω+ω+ω→4ω的共同贡献.     

BiTiO3电子结构及光学性质的第一性原理研究

采用基于第一性原理的赝势平面波方法, 对BiTiO₃的多种结构进行了计算. 计算结果表明, C1C1结构最为稳定, 对应晶格参数为a=b=5.606 Å, c=9.954 Å; α=β=105.1°, γ=61.2°. 进一步对C1C1结构的BiTiO₃的能带结构、电子性质和光学性质进行了研究, 发现BiTiO₃是间接带隙半导体, 其费米面附近的能带主要由Ti-3d和O-2p层的电子态构成. 通过介电函数、复折射率和反射率等的研究, 发现BiTiO₃的光学性质为近各向同性.     

稠苯芳杂环及其烷基质子化学位移的计算

本文提出了予测稠苯芳杂环及其烷基链上质子化学位移的计算方法。 将稠苯芳杂环化合物用凯库勒式表示,计算式为为需考虑的苯环内的乙烯基效应。σ_mi,ci为各苯环的环流效应。σ_1,Hc为各芳杂环的屏蔽效应,对杂环上质子它就是该单独芳杂环上相应质子的δ值,对苯环上质子要将它分解为各结构因素的效应,即:σ_1,He=(1/2)^d-1δ_x=y(或σ_z)+σ_c-c·σ_m,H. σ_x-y与σ_z为杂原子或其基团的屏蔽效应,σ_c=c为存在于芳杂环中的乙烯基的效应,σ_m,Hc为芳杂环的环流效应,d为对不同质子所考虑的键数。有取代基时需考虑取代基的效应。计算环上烷基质子的公式为:δ=σ_p,CH3+ασ_c,CH3+βσ_t,CH3+σ_l,G σ_l,G为稠苯芳杂环基的某级效应。     

反应物NO的振动激发对反应C(3P)+NO(X2Π)→CO(X1Σ+)+N(2D)立体动力学性质的影响

采用准经典轨线方法研究碰撞能为0.23 eV时,反应物分子NO在不同初始振动态(v=0～3)下发生在两个电子态(2A″和2A′)势能面上反应C(3P)+NO(X2Π)→CO(X1Σ+)+N(2D)的立体动力学性质.计算反应产物的转动角动量矢量分布(P(θr)和P(?r))以及微分散射截面(P00(ωt),(P)20(ω...     

Effects of collision energy and rotational quantum number on stereodynamics of the reactions:H(~2S)+NH(v=0,j=0,2,5,10)→N(~4S)+H_2

The stereodynamical properties of H(~2S) + NH(v = 0,j = 0,2,5,10)→N(~4S) + H_2 reactions are studied in this paper by using the quasi-classical trajectory(QCT) method with different collision energies on the double many-body expansion(DMBE) potential energy surface(PES)(Poveda L A and Varandas A J C 2005 Phys.Chem.Chem.Phys.7 2867).In a range of collision energy from 2 to 20 kcal/mol,the vibrational rotational quantum numbers of the NH molecules are specifically investigated on v = 0 and j = 0,2,5,10 respectively.The distributions of P(θ_r),P(φ_r),P(θ_r,φ_r),(2π/σ)(dσ_(00)/dω_t)differential cross-section(DCSs) and integral cross-sections(ICSs) are calculated.The ICSs,computed for collision energies from 2 kcal/mol to 20 kcal/mol,for the ground state are in good agreement with the cited data.The results show that the reagent rotational quantum number and initial collision energy both have a significant effect on the distributions of the k-j',the k-k'-j',and the k-k' correlations.In addition,the DCS is found to be susceptible to collision energy,but it is not significantly affected by the rotational excitation of reagent.     

Creation of multi-frequency terahertz waves by optimized cascaded difference frequency generation

A new scheme which generates multi-frequency terahertz (THz) waves from planar waveguide by the optimized cascaded difference frequency generation (OCDFG) is proposed. A THz wave with frequency ω_T1 is generated by the OCDFG with two infrared pump waves, and simultaneously a series of cascaded optical waves with a frequency interval ω_T1 is generated. The THz wave with a frequency of M-times ω_T1 is generated by mixing the m-th-order and the (m+M)-th-order cascaded optical wave. The phase mismatch distributions of cascaded difference frequency generation (CDFG) are modulated by changing the thickness of planar waveguide step by step, thereby satisfying the phase-matching condition from first-order to high-order cascaded Stokes process step by step. As a result, the intensity of THz wave can be enhanced and modulated by controlling the cascading order of OCDFG.     

Gilbert damping in the layered antiferromagnet CrCl3

We theoretically and experimentally studied the Gilbert damping evolution of both acoustic and optical magnetic resonance modes in the layered flake Cr Cl;with an external magnetic field H applied in plane.Based on a Lagrangian equation and a Rayleigh dissipation function,we predicted that the resonance linewidth△H as a function of microwave frequencyωis nonlinear for both acoustic and optical modes in the Cr Cl;flake,which is significantly different from the linear relationship of△H-ωin ferromagnets.Measuring the microwave transmission through the Cr Cl;flake,we obtained theω–H dispersion and damping evolution△H–ωfor both acoustic and optical modes.Combining both our theoretical prediction and experimental observations,we concluded that the nonlinear damping evolution△H–ωis a consequence of the interlayer interaction during the antiferromagnetic resonance,and the interlayer Gilbert dissipation plays an important role in the nonlinear damping evolution because of the asymmetry of the non-collinear magnetizaiton between layers.     

Properties of strong-coupling magneto-bipolaron qubit in quantum dot under magnetic field

Based on the variational method of Pekar type, we study the energies and the wave-functions of the ground and the first-excited states of magneto-bipolaron, which is strongly coupled to the LO phonon in a parabolic potential quantum dot under an applied magnetic field, thus built up a quantum dot magneto-bipolaron qubit. The results show that the oscillation period of the probability density of the two electrons in the qubit decreases with increasing electron–phonon coupling strength α, resonant frequency of the magnetic field ω_c, confinement strength of the quantum dot ω_0, and dielectric constant ratio of the medium η; the probability density of the two electrons in the qubit oscillates periodically with increasing time t, angular coordinate φ_2, and dielectric constant ratio of the medium η; the probability of electron appearing near the center of the quantum dot is larger, and the probability of electron appearing away from the center of the quantum dot is much smaller.     

Effect of lateral structure parameters of SiGe HBTs on synthesized active inductors

The effect of lateral structure parameters of transistors including emitter width, emitter length, and emitter stripe number on the performance parameters of the active inductor(AI), such as the effective inductance Ls, quality factor Q,and self-resonant frequency ω_0 is analyzed based on 0.35-μm Si Ge Bi CMOS process. The simulation results show that for AI operated under fixed current density JC, the HBT lateral structure parameters have significant effect on Ls but little influence on Q and ω_0, and the larger Ls can be realized by the narrow, short emitter stripe and few emitter stripes of Si Ge HBTs. On the other hand, for AI with fixed HBT size, smaller JCis beneficial for AI to obtain larger Ls, but with a cost of smaller Q and ω_0. In addition, under the fixed collector current IC, the larger the size of HBT is, the larger Ls becomes, but the smaller Q and ω_0 become. The obtained results provide a reference for selecting geometry of transistors and operational condition in the design of active inductors.     

TiO$lt;sub$gt;2$lt;/sub$gt;纳米管电子结构和光学性质的第一性原理研究

运用基于密度泛函理论的第一性原理方法, 系统研究了小尺寸锐钛矿相(n,0)型TiO₂纳米管(D<16 Å)的几何构型、电子结构和光学性质. 结果表明: 随着管径增大, 体系单位TiO₂分子的形成能降低, 体系趋于稳定; 在管径14 Å左右, (n,0)型TiO₂纳米管会发生一次构型的转变. 能带分析显示, TiO₂纳米管的电子态比较局域化, 小管径下(D<14 Å)其导电性更好; 随着构型的转变, TiO₂纳米管由直接带隙转变为间接带隙, 并且带隙值随着管径的增大而增大, 这是由于π轨道重叠效应的影响大于量子限域效应所导致的结果. 两种效应的竞争, 使得TiO₂纳米管的介电函数虚部ε₂ (ω)谱的峰值位置随管径增大既可能红移也可能蓝移, 管径大于9 Å (即(8, 0)管)之后, TiO₂纳米管的光吸收会出现明显的增强. 关键词： 2纳米管')" href="#">TiO₂纳米管 第一性原理 电子结构 光学性质     

稠苯芳环及其烷基质子化学位移的计算

本文提出了予测稠苯芳烃及其衍生物的环上和烷基链上质子化学位移的计算方法。 将稠苯芳环化合物用凯库勒式表示,用下式计算: δ=σ_j.c-c+σ_mi.ci σ_j.c-c为各种乙烯基的效应。σ_mi.ci,为各个苯环的六电子π轨道的净环流效应,其计算式为: σ_m.e=(1/2)^m×1,52 m=n-u m为净环流效应级数,等于质子到该苯环相隔的键数n减其中的顺式键数u。 在菲环和类似菲环的4,5位与9,10位质子需考虑菲环效应。蒄环上的质子需考虑蒄环效应。有取代基需考虑取代基的效应。 计算环上烷基质子的公式: δ=σ_p.CH3+ασ_2.CH3+βσ_t.CH3+σ_i.G 此公式在作者以前的文章中己经报道。σ_i,G为稠苯芳基的某级效应。     

Analytical solutions for a doubly driven two-level atom

We have deduced analytical solutions of an energy level diagram of the doubly driven/dressed atom for a two-level atom exposed to a strong near-resonant bichromatic laser field in a special case, i.e., the bichromatic field with frequencies ω1 and ω2, and Rabi frequencies ?1 and ?2, in which the first coupling field of ?1 acts on the bare atomic levels, and then the resulting singly dressed states are driven by the second coupling field of ?2, thus resulting in the doubly dressed atom.We have measured the probe absorption spectra of a doubly driven two-level atom. The system consists of 52S1/2, F= 2 and 5~2P_(3/2), F'= 3 states of ~(87)Rb atoms in a magneto-optical trap(MOT) as well as the cooling/trapping beams and an additional coupling field. As for the spectroscopic properties of the doubly driven two-level atom, theoretical analytical solutions are in general agreement with the experimental spectrum as a whole.     

Li2C2中电声耦合及超导电性的第一性原理计算研究

通过第一性原理密度泛函和超导Eliashberg理论计算, 我们研究了Li₂C₂在Cmcm相的电子结构和电声耦合特性, 预言这种材料在常压和5GPa下是由电声耦合导致的转变温度分别为13.2 K 和9.8 K的超导体, 为实验上探索包含一维碳原子链的材料中是否可能存在超导电性、发现新的超导体提供了理论依据. 如果理论所预言的Li₂C₂超导电性得到实验的证实, 这将是锂碳化物中转变温度最高的超导体, 高于实验观测到的LiC₂的1.9 K和理论预言的单层LiC₆的8.1 K超导转变温度.     

镁基合金自由枝晶生长的相场模拟研究

利用定量相场模型, 以Mg-0.5 wt.%Al合金为例模拟了基面((0001)面)内镁基合金的等温自由枝晶生长过程. 通过研究该合金体系数值模拟的收敛性, 获得了最优化值耦合参数λ = 5.5及网格宽度Δx/W₀ = 0.4, 并在该参数下系统研究了各向异性强度和过饱和度对枝晶尖端生长速度、尖端曲率半径、Péclet数及稳定性常数σ^* 的影响. 结果表明, 由微观可解性理论得到的稳定性系数σ^* 与ε₆ 拟合值σ^*≅ ε₆ ^1.81905, 更接近理想值σ ^* (ε₆) ≅ε₆ ^1.75. 此外, 当过饱和度Ω < 0.6时, 稳定性系数σ ^* 不随ε₆ 的变化而变化, 而当Ω > 0.6时, 稳定性系数σ ^* 随着ε₆ 的增加而减小. 这反映了枝晶的生长由扩散控制向动力学控制的转变. 随着过饱和度的增加, 枝晶形貌由雪花状枝晶向圆状枝晶转变.     

自驱动Janus微球近壁运动特性实验与数值模拟研究

自驱动Janus微球是形状规则但表面构成不同的特殊活性颗粒. 针对微米级Pt-SiO₂型Janus 微球近壁面自驱动现象, 实验测得了微球的自驱动速度V_Janus, 并观察到微球运动过程中与垂直方向存在一偏转仰角ψ, 且ψ角随H₂O₂溶液浓度的增大呈减小趋势. 在此基础上, 建立自驱动Janus微球的数值模型, 通过模拟得到了微球在不同浓度H₂O₂溶液中的偏转仰角ψ及距底面的高度δ, 模拟与实验一致. 利用这些数据进一步讨论了壁面效应对微球旋转特征时间τ_R的影响. 这一工作对于理解Janus 微球的运动机理及发展相关应用具有重要意义.     

BaTi2Bi2O的电子结构与磁性

采用第一性原理方法,对BaTi₂Bi₂O的电子结构和磁性进行计算.非磁性态的计算结果显示:费米能级处的态密度主要来自d_z²,d_x²-y²和d_xy三个轨道,同时费米面也主要有三部分组成,并且将其沿着矢量q₁=(π/a,0,0)和q₂=(0,π/a,0)平移时,第三部分费米面(沿着X-R连线)与第一部分费米面(M-A连线)嵌套明显,计算得出磁化系数χ₀(q)在X点出现峰值,与峰值出现在M点的FeAs基超导体不同.上述磁化率峰值可以诱导产生自旋密度波,使得BaTi₂Bi₂O材料的磁性基态是bi-collinear antiferromagnetism(AF3)与blocked checkerboard antiferromagnetism(AF4)的二度简并态.随着空穴掺杂,χ₀(q)的峰值降低,而电子掺杂则导致峰值变大.当自旋涨落被完全压制时,超导出现,这可以解释为什么超导只出现在空穴掺杂型化合物而非电子掺杂型.     

NFX(X=-1,0,+1)分子离子基态的结构与势能函数

用密度泛函理论的B3LYP方法,分别以6-311++g(df,3pd),6-311g(3d,3p)和6-311++g(3df,3pd)为基函数对NF分子、NF⁺和NF^-离子基态进行几何优化和频率计算,并进行单点能扫描计算.用最小二乘法拟合得到NF^X(X=-1,0,+1)分子离子基态的Murrell-Sorbie势能函数.利用得到的解析势能函数计算出的NF分子和NF⁺离子基态光谱常数(B_e,α_e,ω_e,ω_eχ_e)与实验值符合很好.首次得到NF^-离子基态的光谱常数(B_e,α_e,ω_e,ω_eχ_e)和力常数(f₂,f₃,f₄),为NF-离子基态的后期研究提供理论参考.     

PS自由基X2Π态的势能曲线和光谱性质

采用Davidson修正的内收缩多参考组态相互作用方法(icMRCI+Q) 结合Dunning等的相关一致基计算了PS自由基X²Π 态势能曲线. 利用三阶Douglas-Kroll Hamilton近似结合cc-pV5Z相对论收缩基进行了相对论修正计算. 利用aug-cc-pCV5Z基组对势能曲线进行了核价相关修正计算, 并将总能量外推至完全基组极限. 拟合得到了X²Π态的主要光谱常数R_e, ω_e, ω_ex_e, ω_ey_e, B_e, α_e 和D_e, 与实验结果符合较好. 利用Breit-Pauli算符, 研究了旋轨耦合效应对势能曲线的影响, 得到了两条Ω 态的势能曲线. 详细分析了在旋轨耦合计算中, 核电子相关与冻结核近似对电子结构和光谱性质的影响. 在icMRCI+Q/56+DK+CV+SO理论水平上得到了两个Ω 态的主要光谱常数T_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e 和α_e, 结果与实验结果一致. 在平衡位置处, 本文的X²Π态旋轨耦合能量分裂值为 323.73 cm^-1, 与实验结果321.93 cm^-1较为一致. 通过求解双原子分子核运动的径向Schrödinger方程, 找到了无转动PS自由基X²Π态及其两个Ω 态的全部振动态, 还分别计算了它们相应的振动能级和惯性转动常数等分子常数, 这些结果与已有的实验值一致. 关键词： 势能曲线 光谱常数 分子常数 旋轨耦合