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.     

Study of valence states of the CO2 molecule by (e, 2e) momentum spectroscopy

The (e, 2e) technique has been used to measure the binding energy spectrum and the momentum distribution of the electrons in the CO₂ molecule outer orbitals. The innermost valence states 2σ_u and 3σ_g have been localized 2 eV away from each other and evidence of configuration interaction involving 3σ_g has been found. The electron momentum distributions for the various orbitals show poor agreement with the square of the Hartree-Fock wave function Fourier transform.     

Conformation effects on the molecular orbitals of serine

This paper calculates the five most stable conformers of serine with Hartree--Fock theory, density functional theory (B3LYP), Moller--Plesset perturbation theory (MP4(SDQ)) and electron propagation theory with the 6-311++G(2d,2p) basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Ser1 by rotation of C₂--C₃ (Ser4), C₁--C₂ (Ser5) and C₁--O₂ (Ser2 and Ser3). Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.     

探测二茂铁外价轨道(e,2e)反应中的扭曲波效应

利用第三代高效率电子动量谱仪,分别在600和1500 eV两种不同入射电子能量下获得了二茂铁(ferrocene)分子外价轨道的电离能谱和电子动量谱的相关实验结果.并利用非相对论与标量相对论密度泛函方法计算出了二茂铁的重叠型和交错型两种不同构象的理论动量谱.两种构象的外价轨道一一对应,理论电子动量谱基本一样.对二茂铁的外价轨道,在低动量区观测到了强烈的扭曲波效应,这与这些轨道主要由铁原子的3d轨道构成有关.通过相对论和非相对论计算结果的比较,表明相对论效应对于二茂铁的外轨道动量分布几乎没有影响. 关键词： 二茂铁分子 电子动量谱 相对论效应 扭曲波效应     

Penning ionization electron spectroscopy and photo-electron spectroscopy of molecular solids. II. Ammonia and water

The Penning ionization electron spectra (PIES) and ultraviolet photoelectron spectra (UPS) of ammonia and water molecules condensed on a cold metal substrate have been measured using thermal He*(2³S, 2¹S) metastable atoms and He(I) (58.4 nm) photons. The shifts of the observed positions of the PIES peaks relative to those of the UPS peaks in the condensed phase are roughly equal to the corresponding shifts in the gas phase. The relative intensities of the 3a₁ and 1e orbital peaks are reversed in the PIES and UPS for both gaseous and condensed ammonia; the origin of this reversal is interpreted as the difference between the interactions with metastable atoms and photons. On the other hand, the relative intensities of the 3a₁ orbital peak in the PIES and UPS for condensed water decrease as compared to the gas-phase spectra. This implies participation of the 3a₁ orbital of water in the hydrogen bonding.     

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.     

The temperature dependence of penning ionization electron energy spectra: He(23S)—ar,N2, NO,O2, N2O,CO2

Using two intense thermal energy He(2³S) sources of different temperatures (≈400 and ≈ 1000 K, resp.) and a transmission-calibrated electron energy analyzer with about 30meV resolution, the dependence of He(2³S) Penning ionization electron spectra on collision energy for the target species Ar, N₂, NO, O₂, N₂O and CO₂ have been studied. The energy shifts of the Penning electron energy distributions and the branching ratios for the population of different electronic states in the molecular ions are determined quantitatively and compared for the two different collision temperatures. These results and the shapes of the observed Penning electron energy distributions are discussed in the light of current models for the Penning procen; the observed temperature dependences are correlated with the nature of the ionized orbitals in cases of only one entrance channel (closed shell targets) and, in addition, to the existence of qualitatively different entrance channels (open shell targets).     

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.     

SF6电子动量谱学研究中干涉效应的观测

利用非共面对称的高效率(e,2e)电子动量谱仪测量了SF₆分子外价分子轨道的二维电子能量- 动量密度谱. 通过理论计算与实验结果的比较,发现B3LYP密度泛函理论计算结果可以较好地解释实验测量的轨道电子动量分布. 此外,对于最外层的4个来自F2p孤对电子贡献的非键分子轨道,实验上观测到非常明显的多中心干涉图样.     

Two-dimensional Penning ionization electron spectroscopic study on outer characteristics of molecules

Collision-energy/electron-energy-resolved two-dimensional Penning ionization electron spectroscopy (2D-PIES) has been used to study outer characteristics of molecules. Anisotropic potential energy surfaces for collisional ionization of molecules with a metastable helium atom He*(2³S) have been determined starting from ab initio model potentials via optimization based on trajectory calculations. Since ionization widths in the theoretical model of Penning ionization are functionals of target molecular orbitals, outer electron distributions of molecular orbitals can be determined via optimization procedures of calculated ionization cross-sections by trajectory calculations with respect to observed 2D-PIES data.     

(e, 2e) spectroscopy of N2—valence momentum distributions and configuration interaction

The noncoplanar symmetric (e, 2e) reaction has been applied to N₂ at 1200, 600 and 400 eV. Separation energy spectra are obtained in the valence region, the observed structure extending to above 60 eV. Electron momentum profiles are measured at a number of separation energies. They agree very well with the momentum distributions for valence orbitals given by SCF calculations. Considerable configuration interaction structure is observed, being primarily due to configuration interaction in the 2σ_g hole state. At 1200 eV the spectroscopic sum rule is satisfied within experimental error, confirming the validity of the analysis.     

Electron momentum spectroscopy of the highest occupied molecular orbitals of chlorobromomethane

The first measurement of the complete valence shell binding energy spectra of chlorobromomethane (CH₂ BrCl) is reported by (e, 2e) electron momentum spectrometer using symmetric non-coplanar geometry at an impact energy of 1200 eV plus binding energy. The experimental electron momentum profiles of the highest occupied molecular orbitals (HOMOs) are extracted and compared with Hartree-Fock (HF) and density functional theory (DFT) calculations. DFT calculation employing B3LYP hybrid functional and the large-sized basis sets provides the best agreement with the experiment.     

(e,2e) Spectroscopy of ethane

The 400-eV and 1200-eV non-coplanar symmetric (e, 2e) reaction has been used to measure the momentum distributions of electrons in the individual valence orbitals of ethane as well as to measure the complete separation energy spectra in the valence region. The shapes and relative magnitudes of the momentum distributions agree well with those calculated using the plane wave off-shell impulse approximation and double zeta basis molecular orbital wave functions. The ground state of C₂H₆⁺ is shown to be 1e_g^?1, with the vertical ionization potential being 12.25 ± 0.1 eV. Considerable structure due to configuration interaction is observed in the separation energy region 29–55 eV. Much of this structure can be assigned to the 2a_1g orbital.     

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     

Identification of singlet excited electronic states of hydroxybenzoic acid isomers

The photoelectron spectra of benzoic and para-, meta-, and ortho-hydroxybenzoic acids and their UV absorption spectra in ethanol are obtained. The photoelectron spectra in the energy region up to 15.5 eV are interpreted based on the B3LYP/6-311+G(d, p) calculations. Based on the TDDFT B3LYP/6-311+G(d, p) calculations and taking into account the obtained interpretation of photoelectron spectra, the UV absorption bands are assigned to particular singlet transitions. For each transition, the electron configuration that makes the main contribution to the transition is determined. It is shown that the transition energy depends on the energy gap between the corresponding occupied and unoccupied molecular orbitals.     

Electron momentum distributions and binding energies for the valence orbitals of hydrogen bromide and hydrogen iodide

Electron binding energy spectra and momentum distributions have been obtained for the valence orbitals of HBr and HI using noncoplanar symmetric electron coincidence spectroscopy at 1200 eV. The weakly bonding inner valence ns orbitals, which have not been observed previously, have their spectroscopic (pole) strength severely split among a number of ion states. For HBr the strength of the “main” inner valence (ns) transition is 0.42±0.03 whereas for HI it is 0.37±0.04, in close agreement with the value observed for the valence s orbitals of the corresponding isoelectronic inert-gas atoms. The spectroscopic strength for the two outermost orbitals is found to be close to unity, in agreement with many-body Green's function calculations. The measured momentum distributions are compared with several spherically averaged MO momentum distributions, as well as (for HBr) with a Green's function calculation of the generalized overlap amplitude (GOA). The GOA momentum distributions are in excellent agreement with the HBr data, both in shape and relative magnitude. Not all of the MO momentum distributions are in reasonable agreement with the data. Comparison is also made with the calculated momentum distributions for Kr, Br, Xe and I.     

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     

Study of molecular orbitals by means of (e,2e) spectroscopy on oriented molecules

The usefulness of the (e,2e) technique applied to the study of the electron momentum density for orbitals oriented in space is discussed. Calculations on N₂ and CO are used to show the potential usefulness of this technique in investigating the bonding properties of molecules. A brief mention of those phenomena in which oriented molecules are involved is made.     

UF_6分子价轨道相对论效应的理论电子动量谱学研究

用非相对论、标量相对论和二分量相对论三种不同的密度泛函方法对UF_6分子的电子结构进行了量子化学计算,并利用编写的程序计算出了三种方法下各个价轨道的电子动量谱,比较了三种方法计算的价轨道能级及动量分布的差异.结果表明,相对论效应不仅使UF_6的能级劈裂和移动,而且对部分价轨道电子动量分布有显著的影响.