Experimental and theoretical investigations into the electronic structure of CF2Br2 by electron momentum spectroscopy

The binding energy spectra and electron momentum density distributions for the valence orbitals of CF₂Br₂ have been obtained by using electron momentum spectroscopy (EMS) at an impact energy of 1200 eV plus binding energy. The measured electron momentum profiles are compared with Hartree–Fock (HF) and density functional theory (DFT) calculations with different-sized basis sets. In general, the DFT-B3LYP calculation using the large basis sets of 6-311++G** and aug-cc-pVTZ fairly describe the experimental results. Moreover, the controversial orderings of the outer valence orbitals have been reassigned. The pole strength of the main ionization transition from the inner valence orbital of 1b₂ is determined.     

环戊烯分子内价轨道1a′的电子动量谱学研究

报道了环戊烯（C₅H₈）分子1a′轨道的电子动量谱，并且给出了价 轨道的电离能谱信息 .实验在非共面对称几何条件下用能量多道型电子动量谱仪完成，入射电子的能量为1200 eV 加结合能.通过Hartree-Fock 和密度泛函方法计算得到了C₅H₈分子 1a′轨道的动量谱. 对1a′轨道的电子动量谱的实验值和理论计算进行了比较，得到了该轨道的极强度（pole s trength）的信息.     

环戊烯分子内价轨道1a′的电子动量谱学研究

报道了环戊烯（C₅H₈）分子1a′轨道的电子动量谱，并且给出了价 轨道的电离能谱信息 .实验在非共面对称几何条件下用能量多道型电子动量谱仪完成，入射电子的能量为1200 eV 加结合能.通过Hartree-Fock 和密度泛函方法计算得到了C₅H₈分子 1a′轨道的动量谱. 对1a′轨道的电子动量谱的实验值和理论计算进行了比较，得到了该轨道的极强度（pole s trength）的信息.     

用(e, 2e)电子碰撞电离测量乙烯分子中的扭曲波效应

利用新一代高性能（e,2e）电子动量谱仪,在400—2400 eV的大范围入射电子能量条件下,测量了乙烯分子电子密度的动量分布.实验测量的乙烯1b3g轨道电子动量分布与平面波冲量近似的理论计算结果相比,在低动量区和高动量区出现明显的上翘（turn up）效应,并且此上翘效应随着入射电子能量的增加而逐渐减小.进一步的分析证实由于分子的扭曲波效应引起1b3g轨道动量分布在低动量区和高动量区的上翘.实验测量结果将对分子扭曲波理论计算的建立提供实验依据.     

N2价轨道的精细电子动量谱学研究

在高分辨率（ΔE=08?eV,Δp≈01a.u.）高效率的第三代电子动量谱仪上获得了N₂价轨道的电离能谱和动量谱.通过对伴线结构的电子动量谱学（EMS）研究,得到了不同伴线结构的电子动量谱,另一方面也得到了伴线结构的强度.由伴线的电子动量分布形状判断出其跃迁的主要来源,并由实验测量的伴线结构强度确定了谱因子（极强度）的大小,通过对谱因子实验值与理论计算结果的比较检验了各种理论模型的精确度. 关键词： 氮分子 价轨道 电子动量谱 电子关联效应     

用(e,2e)电子碰撞电离测量乙烯分子中的扭曲波效应

利用新一代高性能（e,2e）电子动量谱仪,在400-2400 eV的大范围入射电子能量条件下,测量了乙烯分子电子密度的动量分布.实验测量的乙烯1b3g轨道电子动量分布与平面波冲量近似的理论计算结果相比,在低动量区和高动量区出现明显的上翘（turn up）效应,并且此上翘效应随着入射电子能量的增加而逐渐减小.进一步的分析证实由于分子的扭曲波效应引起1b3g轨道动量分布在低动量区和高动量区的上翘.实验测量结果将对分子扭曲波理论计算的建立提供实验依据.     

二乙酰分子内价轨道4ag+4bu的电子动量谱学研究

在高分辨率(ΔE=115eV, Δp≈01a.u.)电子动量谱仪上获得了二乙酰分子(d iacetyl)最内价轨道4ag_g+4bu_u的电离能谱和动量谱的实验结果， 并用Hartree-Fock和密度泛函理论方法做了理论计算.实验结果与理论计算符合较好. 关键词： 二乙酰 内价轨道 电离能 电子动量谱     

The effective ionization coefficients and electron drift velocities in gas mixtures of CF3I with N2 and CO2 obtained from Boltzmann equation analysis

The electron swarm parameters including the density-normalized effective ionization coefficients(α-η)/N and the electron drift velocities V e are calculated for a gas mixture of CF3I with N2 and CO2 by solving the Boltzmann equation in the condition of a steady-state Townsend(SST) experiment.The overall density-reduced electric field strength is from 100 Td to 1000 Td(1 Td = 10-17V·cm2),while the CF3I content k in the gas mixture can be varied over the range from 0% to 100%.From the variation of(αη)/N with the CF3I mixture ratio k,the limiting field strength(E/N) lim for each CF3I concentration is derived.It is found that for the mixtures with 70% CF3I,the values of(E/N) lim are essentially the same as that for pure SF 6.Additionally,the global warming potential(GWP) and the liquefaction temperature of the gas mixtures are also taken into account to evaluate the possibility of application in the gas insulation of power equipment.     

用于白光LED的高亮度蓝白色荧光粉Ca2SiO3Cl2：Eu2+的发光性质

采用固相法在较低温度下合成了Eu²⁺激活的Ca₂SiO₃Cl₂高亮度蓝白色发光材料,并对其发光性质进行了研究。其发射光谱由两个谱带组成,峰值分别位于420,498nm处,归结为Ca₂SiO₃Cl₂晶体中占据两种不同Ca²⁺格位的Eu²⁺离子的5d→4f跃迁发射。改变Eu²⁺浓度,可以使样品的发光在蓝白色和绿白色之间变化。当Eu²⁺浓度为0.005mol^-1时,样品呈现很亮的蓝白色发光。两个发射峰的激发光谱均分布在250~410nm的波长范围内,峰值分别位于333,369nm处。Ca₂SiO₃Cl₂:Eu²⁺可被InGaN管芯产生的近紫外辐射有效激发,是一种性能良好的白光LED用单一基质蓝白色荧光粉。     

Local trimer orbital ordering in LiNiO2 studied by quantitative convergent beam electron diffraction technique

A local trimer orbital ordering model of LiNiO₂ was studied by means of theoretical calculation and experimental measurement of electron structure factors. Based on the trimer model, the electron structure factors were calculated by using the scattering factor of non-spherical Ni³⁺ ion. From these results, it is found that the effect of local orbital ordering on the electron structure factors of several subtle reflections, such as (202) and (107), is very large. The electron structure factors of these subtle reflections were measured by quantitative convergent beam electron diffraction method. The experimentally measured electron structure factor values of these reflections indicate that the trimer orbital ordering model is more close to the true structure of LiNiO₂.     

Capability of Raman lidar for monitoring the variation of atmospheric CO2 profile

Lidar （Light detection and ranging） has special capabilities for remote sensing of many different behaviours of the atmosphere. One of the techniques which show a great deal of promise for several applications is Raman scattering. The detecting capability, including maximum operation range and minimum detectable gas concentration is one of the most significant parameters for lidar remote sensing of pollutants. In this paper, based on the new method for evaluating the capabilities of a Raman lidar system, we present an evaluation of detecting capability of Raman lidar for monitoring atmospheric CO2 in Hefei. Numerical simulations about the influence of atmospheric conditions on lidar detecting capability were carried out, and a conclusion can be drawn that the maximum difference of the operation ranges caused by the weather conditions alone can reach about 0.4 to 0.5km with a measuring precision within 30ppmv. The range of minimum detectable concentration caused by the weather conditions alone can reach about 20 to 35 ppmv in vertical direction for 20000 shots at a distance of 1 km on the assumption that other parameters are kept constant. The other corresponding parameters under different conditions are also given. The capability of Raman lidar operated in vertical direction was found to be superior to that operated in horizontal direction. During practical measurement with the Raman lidar whose hardware components were fixed, aerosol scattering extinction effect would be a significant factor that influenced the capability of Raman lidar. This work may be a valuable reference for lidar system designing, measurement accuracy improving and data processing.     

Spin polarization effect for Co2 molecule

The density functional theory (DFT)(b3p86) of Gaussian 03 has been used to optimize the structure of the Co$_{2}$ molecule, a transition metal element molecule. The result shows that the ground state for the Co$_{2}$ molecule is a 7-multiple state, indicating a spin polarization effect in the Co$_{2}$ molecule. Meanwhile, we have not found any spin pollution because the wavefunction of the ground state is not mingled with wavefunctions of higher-energy states. So for the ground state of Co$_{2}$ molecule to be a 7-multiple state is the indicative of spin polarization effect of the Co$_{2}$ molecule, that is, there exist 6 parallel spin electrons in a Co$_{2}$ molecule. The number of non-conjugated electrons is the greatest. These electrons occupy different spacial orbitals so that the energy of the Co$_{2}$ molecule is minimized. It can be concluded that the effect of parallel spin in the Co$_{2}$ molecule is larger than the effect of the conjugated molecule, which is obviously related to the effect of electron d delocalization. In addition, the Murrell--Sorbie potential functions with the parameters for the ground state and the other states of the Co$_{2}$ molecule are derived. The dissociation energy $De$ for the ground state of Co$_{2}$ molecule is 4.0489eV, equilibrium bond length $R_{\rm e}$ is 0.2061~nm, and vibration frequency $\omega _\e $ is 378.13~cm$^{ - 1}$. Its diatomic molecule force constants $f_2$, $f_3$, and $f_4$ are 2.4824~aJ$\cdot$nm$^{ - 2}$, -7.3451~aJ$\cdot$nm$^{ - 3}$, and 11.2222~aJ$\cdot$nm$^{ - 4 }$respectively(1~aJ=$10^{-18}$~J). The other spectroscopic data for the ground state of Co$_{2}$ molecule $\omega_{\e}\chi _{\e}$, $B_{\e}$, and $\alpha_{\e}$ are 0.7202~cm$^{-1}$, 0.1347~cm$^{-1 }$, and 2.9120$\times $ 10$^{-1}$~cm$^{-1}$ respectively. And $\omega_{\e}\chi _{\e}$ is the non-syntonic part of frequency, $B_{\e}$ is the rotational constant, $\alpha_{\e}$ is revised constant of rotational constant for non-rigid part of Co$_2$ molecule.     

Resonant excitation of a new valence state in N2 by electron impact

A new valence state which lies below the first Rydberg state has been observed in N₂, in the 11.3 to 12.1 eV energy range, using an electron impact technique. This state is only excited from 1.3 to ～3 eV above its threshold through a short lived resonance. Some levels are not clearly resolved but their presence is deduced from the resonant profiles of their differential cross sections. A perturbation in the relative intensities of the C³Π_u vibrational levels is observed when this new state is excited.     

Spin polarization effect for molecule Ta2

Density functional theory （DFT） （B3p86） has been used to optimize the structure of the molecule Ta2. The result shows that the ground state of molecule Ta2 is a 7-multiple state and its electronic configuration is ^7∑u^＋, which shows the spin polarization effect for molecule Ta2 of transition metal elements for the first time. Meanwhile, spin pollution has not been found because the wavefunction of the ground state does not mix with those of higher states. So, the fact that the ground state of molecule Ta2 is a 7-multiple state indicates a spin polarization effect of molecule Ta2 of the transition metal elements, i.e. there exist 6 parallel spin electrons and the non-conjugated electrons are greatest in number. These electrons occupy different space orbitals so that the energy of molecule Ta2 is minimized. It can be concluded that the effect of parallel spin of the molecule Ta2 is larger than the effect of the conjugated molecule, which is obviously related to the effect of d-electron delocalization. In addition, the Murrell-Sorbie potential functions with parameters for the ground state ^7∑u^＋ and other states of the molecule Ta2 are derived. The dissociation energy De, equilibrium bond length Re and vibration frequency we for the ground state of molecule Ta2 are 4.5513eV, 0.2433nm and 173.06cm^-1, respectively. Its force constants f2, f3 and f4 are 1.5965×10^2aJ.nm^-2, -6.4722×10^3aJ·nm^-3 and 29.4851×10^4aJ·nm^-4, respectively. Other spectroscopic data we xe, Be and αe for the ground state of Ta2 are 0.2078cm^-1, 0.0315 cm^-1 and 0.7858×10^-4 cm^-1, respectively.     

Electron Momentum Distributions for 4a1 Orbitals of CFxCl4-x in Low Momentum Region: a Possible Evidence of Molecular Geometry Distortion

由于低动量区域理论和实验的严重差异,重新分析了系列氟利昂分子CF₃Cl、CF₂Cl₂和CFCl₃ (CF_xCl_4-x, x=1～3)的4a₁轨道的电子动量分布. 利用分子离子的平衡几何构型计算得到的动量分布很大地改善了,与实验数据之间的吻合,这一结果表明在p<0.5 a.u.区域实验观测到的偏高的动量分布值可能是电离瞬间分子构型的扭曲带来的. 进一步的分     

Molecular dynamics study of the ternary compound Li3AlB2O6

A new compound with the stone cheinical composition as Li3AlB2O6 but with a different x-ray powder diffraction pattern as reported before was synthesized and studied experimentally by M. He, Chen X Let al （J. Solid State Chem. 163, 369 （2002））, but there lacks first principles study on the structure of it. Using conjugant gradient （CG） molecule dynamics （MD） simulation with a full relaxation of the atomic positions and of the shape and size of the cell, the structure of Li3AlB2O6 is studied from first principles. For the density functional, the local density approximation （LDA） and the generalized gradient approximation （GGA） forms are used respectively. Both the LDA and GGA results support the experimental structure of M. He et al. The result of MD simulation using GGA agrees with the experimental result much better. The energy bands are also studied, the band gap given by LDA and GGA are 5.65 eV, 5.34eV, respectively.     

电子束在VO2薄膜中引起的价态、相结构和光学性能的改变

 利用能量为1.7MeV, 注量分别为1.25×10¹³/cm², 1.25×10¹⁴/cm², 1.25×10¹⁵/cm²的电子束辐照VO₂薄膜,采用XPS, XRD等测试手段对电子辐照前后的样品进行分析,并研究了电子辐照对样品相变过程中光透射特性的影响。结果表明电子辐照引起VO₂薄膜中V离子出现价态变化现象,并使薄膜的X射线衍射峰发生变化。电子辐照在样品中产生的这些变化显著改变了VO₂薄膜的热致相变光学特性。     

外场作用下C12H4Cl4O2的分子结构和电子光谱研究

各种环境毒物危害着人类的生产生活,二噁英更是严重危害人类的健康.C₁₂H₄Cl₄O₂（2,3,7,8-tetrachlorodibenzo-p-dioxin,TCDD）是二噁英中毒性最强的化合物,也是目前已知毒性最强的污染物.为研究TCDD外场效应,采用密度泛函理论方法优化了不同静电场0–0.025 a.u.（0–1.2856×10¹⁰ V/m）作用下TCDD分子的基态几何结构,得到了分子总能量;在此基础上,采用含时密度泛函理论方法对TCDD分子的紫外-可见（UV-Vis）吸收光谱在不同外电场下的变化进行了研究.结果表明：分子几何构型与电场大小呈现强烈的依赖关系,分子总能量随着外电场的增强而减小;伴随着外电场的增强,分子激发态的摩尔吸收系数逐渐减小,UV-Vis吸收峰显著红移.