Ar原子电离能谱和Ar3p电子动量谱研究

电子动量谱学（ElectronMomentumSPectroscoP则是近．二十年来发展起来的一种新兴的探测原子、分子和固体结构的手段，它不仅能够获得轨道结合能的信息，而且能够能壳分辨地得到轨道电子的动量分布（即动量表象中的波函数模方）；同时它还是研究电子关联的最有效的实验手段．其     

电子动量谱学及其在化学中的应用

电子动量谱学是新近发展起来的一个前沿领域,它在研究原子和分子的结构时,显示出独特的为现有其它方法所没有的优点。在国外已经进行了多年的实验和理论研究,成果相当显著;在国内这一研究也已经在进行中。本文对电子动量谱学的基本原理、基本的实验方法和理论方法、已经取得的进展,以及应用前景作了简要的叙述。     

二氧化碳分子3σu轨道的电子动量谱测量

The electron momentum distribution of 3σu orbital of carbon dioxide has been meas-ured at high momentum resolution.Through comparation between experimental and theoretical results,the calculation by DFT-B3LYP method using 6-311++G* basis set is more agree-ment with the experimental data than other calculations.     

单面桥联手性金属卟啉的合成、构象分析及不对称催化氧化性能

合成并表征了新型单面桥连手性卟啉(1a)及其铁配合物(1b), 利用分子力学方法和1H NMR对手性卟啉的空间构象及手性空腔特征进行了分析. 将化合物1b用于苯乙烯衍生物的催化环氧化反应, 结果表明, 轴向配体的存在使化合物1b获得了较高的对映选择性(e.e.为73%-80％), 反应产率及速率也有大幅度提高, 4-叔丁基吡啶的效果最好. 催化体系中轴向配体控制了反应底物向化合物1b手性空腔的定向趋近, 从而有效地提高了手性催化性能.     

2-芳基-5-(5-苯基-2H-四唑-2-亚甲基-1,3,4- 二唑类化合物的研究

本文研究了用N-(5-苯基-2H-四唑-2-乙酰基)-N'-芳酰肼制备分子中既有四唑, 1,3,4- 二唑环的2-芳基-5-(5-苯基-2H-四唑-2-亚甲基)-1,3,4- 二唑。并对化合物进行了质谱研究。     

丙烷分子的价轨道(2b2)电子的动量分布测量

电子动量谱学（EMS）是在原子、分子和固体物理中研究电子结构的一种强有力的工具，它基于运动学条件完全确定的（e，2e）碰撞电离反应[1-3]．本文报告用高分辨电子动量谱仪首次测量得到丙烷门3H8）分子的价轨道电子（252）的动量分布·丙烷（C3Hs）价轨道电子的动量分布实验是     

碳数规律中((e)A)/((e)(1/r))、( B'')/((e)(1/r))值与固定液极性的关系

采用n-烷烃在不同极性的固定液中,在不同色谱柱温下试验的大量数据表明,碳数规律中A、B'值与柱温倒数(1/T)的关系中,(e)A/(e)(1/T)值随固定液极性增加而增大;(e)B'/(e)(1/T)值随固定液极性增加而减小,即(e)A/(e)(1/T)值与Mertynolder常数成正比;(e)B'/(e)(1/T)值与Mertynolder常数成反比.     

碳数规律中值与固定液极性的关系

采用n-烷烃在不同极性的固定液中,在不同色谱柱温下试验的大量数据表明,碳数规律中A、B'值与柱温倒数(1/T)的关系中,(e)A/(e)(1/T)值随固定液极性增加而增大;(e)B'/(e)(1/T)值随固定液极性增加而减小,即(e)A/(e)(1/T)值与Mertynolder常数成正比;(e)B'/(e)(1/T)值与Mertynolder常数成反比.     

Electron Momentum Spectroscopy of Outer Valence Orbitals of 2-Fluoroethanol

The binding energy spectra and electron momentum distributions for the outer valence molecular orbitals of gaseous 2-fluoroethanol have been measured by the non-coplanar asymmetric (e, 2e) spectrometer at impact energy of 2.5 keV plus binding energy. The quantitative calculations of the ionization energies and the relevant molecular orbitals have been carried out by using the outer-valence Green’s function method and the density functional theory with B3LYP hybrid functional. The observed ionization bands in binding energy spectra, as well as the previous photoelectron spectrum which was not assigned, have been assigned for the first time through the comparison between experiment and theory. In general, the theoretical electron momentum distributions calculated by B3LYP method with aug-cc-pVTZbasis set are in line with the experimental ones when taking into account the Boltzmannweighted thermo-statistical abundances of five conformers of 2-fluoroethanol.     

1-碘丙烷分子的电子动量谱学研究：自旋-轨道耦合效应与分子内轨道相互作用

利用不对称不共面电子动量谱仪,在2.5 keV碰撞能量下,采用高精度的SAC-CI方法计算了1-碘丙烷分子束缚能谱,同时采用Hartree-Fock、B3LYP/aug-cc-pVTZ（C,H）6-311G＊＊（I）方法计算其电子动量分布. 并对电离能峰进行了标示. 结合非相对论与相对论计算方法以及自然键轨道分析,对最外层两个轨道（碘的5p孤对）的自旋-轨道耦合效应与分子内轨道相互作用进行了比较. 两种相互作用对电子动量分布的不同影响是可观的. 实验结果与相对论计算的结果一致,表明1-碘丙烷分子内自旋-轨道耦合效应占主导.     

Observation of Interference Effects in (e, 2e) Electron Momentum Spectroscopy of SF6 (cited: 1)

Two-dimensional electron density map (2D map) of binding energy and relative azimuthal angle (i.e., momentum) for the outer-valence molecular orbitals of SF₆ has been measured by a highly sensitive electron momentum spectrometer with noncoplanar symmetric geometry at the impact energy of 1.2 keV plus binding energy. The experimental electron momentum profiles for the relevant molecular orbitals have been extracted from the 2D map and interpreted on the basis of the quantitative calculations using the density functional theory with B3LYP hybrid functional. For the outermost F2p nonbonding orbitals of SF₆, the interference patterns are clearly observed in the ratios of the electron momentum profiles of molecular orbitals to that of atomic F2p orbital.     

Electron Momentum Spectroscopy of Ethanethiol Complete Valence Shell

The binding energy spectra and electron momentum distributions for the complete valence orbitals of ethanethiol were measured for the first time by binary (e, 2e) electron momentum spectroscopy employing non-coplanar symmetric kinematics at an impact energy of 1200 eV plus binding energy. The experimental results are generally consistent with the theoretical calculations using density functional theory and Hartree-Fock methods with various basis sets. A possible satellite line at 17.8 eV in binding energy spectrum was observed and studied by electron momentum spectroscopy.     

Vibrational effects on the electron momentum distributions of valence orbitals of formamide

The ionization energy spectra and electron momentum distributions of formamide were investigated using the high-resolution electron momentum spectrometer in combination with high level calculations. The observed ionization energy spectra and electron momentum distributions were interpreted using symmetry adapted cluster-configuration interaction theory, outer valence Green function, and DFT-B3LYP methods. The ordering of 10a(') and 2a(") orbitals of formamide was assigned unambiguously by comparing the experimental electron momentum distributions with the corresponding theoretical results, i.e., 10a(') has a lower binding energy. In addition, it was found that the low-frequency wagging vibration of the amino group at room temperature has noticeable effects on the electron momentum distributions. The equilibrium-nuclear-positions-approximation, which was widely used in electron momentum spectroscopy, is not accurate for formamide molecule. The calculations based on the thermal average can evidently improve the agreement with the experimental momentum distributions.     

The outer valance orbital electron densities of cyclopentane by binary (e,2e) spectroscopy

The binding energy spectra and electron distributions in momentum space of the valence orbitals of cyclopentane (C(5)H(10)) are studied by Electron Momentum Spectroscopy (EMS) in a noncoplanar symmetric geometry. The impact energy was 1200 eV plus binding energy and energy resolution of the EMS spectrometer was 1.2 eV. The experimental momentum profiles of the outer valence orbitals are compared with the theoretical momentum distributions calculated using Hartree-Fock and density functional theory (DFT) methods. The shapes of the experimental momentum distributions are generally quite well described by both the Hartree-Fock and DFT calculations when the large and diffuse basis sets are used.     

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

Electron momentum distributions for 4a1 orbitals of serial freon molecules CFaC1, CF2Cl2, and CFCl3 （CFxC14-x, x=1-3） have been reanalyzed due to the severe discrepancies between theory and experiment in low momentum region. The tentative calculations using equilibrium geometries of molecular ions have exhibited a great improvement in agreement with the experimental data, which suggests that the molecular geometry distortion may be responsible for the observed high intensities at p〈0.5 a.u.. Further analyses show that the severe discrepancies at low momentum region mainly arise from the influence of molecular geometry distortion on C-Cl bonding electron density distributions.