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1.
精确的甲烷分子价轨道的电子动量谱学研究   总被引:1,自引:1,他引:0  
电子动量谱学(EMS)已发展成为探测原子分子电子结构的强有力工具.借助电子动量谱学可获得精确的分子轨道电子密度分布,并能提供非常详细的电子运动和电子关联信息.分子电子密度分布和电子运动的详细了解对分子的识别和化学活性的理解非常重要,并且也有助于计算机辅助的分  相似文献   

2.
    
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.  相似文献   

3.
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.  相似文献   

4.
    
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.  相似文献   

5.
电子动量谱仪的研制和He原子结构的研究   总被引:1,自引:1,他引:0  
前文指出,电子动量语学是研究原子和分子结构的一种新方法,其价值在于:它既能直接得到电子能级,又能相当直接和精细地得到各个电子态的动圭分布(屯就是动会表象中的电子波函数模方).这些信息对量子化学等学科是极为有用的.在发达国家,电子动量语学已受到广泛的重视,但在国内还几乎是空白.虽然少数单位正在或准备开展这一工作,然而至今还没有成功的实验报导,其原因是国内还没有电子动量谱仪(Elec-tronM。nt。Spectro。ter,缩写为EMS),它是开展电子动量谱学实验的关键设备,在现阶段的国内外市场上均无产品出售,需要使…  相似文献   

6.
    
The binding energy spectrum and electron momentum profiles of the inner orbitals of methyl iodide have been measured using an electron momentum spectrometer at the impact energy of 1200 eV plus binding energy. Two peaks in the binding energy spectrum, arising from the spin-orbit splitting, are observed and the corresponding electron momentum profiles are obtained. Relativistic density functional calculations are performed to elucidate the experimental electron momentum profiles of two spin-orbit splitting components, showing agreement with each other except for the intensity in low momentum region. The measured high intensity in the low momentum region can be further explained by the distorted wave calculation.  相似文献   

7.
讨论了具有辛群对称性的一类价激发n电子波函数 ψ_(a,s_1,s_2)=N(multiply from t=s_1 to s_1+s_2-1)(a_1+(a_t))(multiply from k=s_1+s_2 to s_1+s_2+m-1)G+(ζ,k,V_(s+1))|0>的性质,它们对闭壳层和开壳层体系均适用.用此类函数计算了Li_2,LiH_2~-和CH_3~+,结果表明这类函数能较好地描述电子相关作用,并且变分得到的轨道都是自然轨道。  相似文献   

8.
以作者所在实验室最近完成的He原子基态的电子动全港学实验结果为基础,对三类He原子基态波函数进行了分析与检验.结果表明,电子动量话学是获取电子波西数信息的有用手段.且实验结果与理论计算的联系文*已报导了本实验室最近完成的He原子基态的电子动量话学实验结果.此实验的条件满足准自由碰撞的要求问,平面波冲量近似是适用的,因而实验测定的(e,Ze)反应的符合计数N可表为问本文自始至终采用原子单位(an),除非另有说明.在(1)中,C是比例常数,只与实验条件有关;PO,PI和马分别是人射电子和两个出射电子的动量,Th是…  相似文献   

9.
The development of a third-generation electron momentum spectrometer with significantly improved energy and momentum resolutions at Tsinghua University (ΔE = 0.45–0.68 eV, Δθ = ±0.53° and Δ? = ±0.84°) has enabled a reinvestigation of the valence orbital electron momentum distributions of H2O with improved statistical accuracy. The measurements have been conducted at impact energies of 1200 eV and 2400 eV in order to check the validity of the plane wave impulse approximation. The obtained ionization spectra and electron momentum distributions have been compared with the results of computations carried out with Hartree Fock [HF] theory, density functional theory in conjunction with the standard B3LYP functional, one-particle Green’s function [1p-GF] theory along with the third-order algebraic diagrammatic construction scheme [ADC(3)], symmetry adapted cluster configuration interaction [SAC-CI] theory, and a variety of multi-reference [MR-SDCI, MR-RSPT2, MR-RSPT3] theories. The influence of the basis set on the computed momentum distributions has been investigated further, using a variety of basis sets ranging from 6-31G to the almost complete d-aug-cc-pV6Z basis set. A main issue in the present work pertains to a shake-up band of very weak intensity at 27.1 eV, of which the related momentum distribution was analyzed for the first time. The experimental evidences and the most thorough theoretical calculations demonstrate that this band borrows its ionization intensity from the 2a1 orbital.  相似文献   

10.
使用B3LYP/TZVP//B3LYP/aug-cc-pVTZ方法系统研究了饱和烷烃分子CnH2n+2(n=4-6)的轨道电子动量光谱,比较了同分异构体CnH2n+2(n=4-6)对轨道动量分布的影响.结合二维空间分析方法对电子在坐标空间中的密度分布进行了系统的研究.计算结果表明,最内价壳层电荷分布主要由s电子贡献,第二近邻芯价壳层则主要由p电子贡献,而其余的价壳层则为sp杂化.最内价轨道表现出最大的谱线强度并且远大于其它轨道的谱线强度,而且正烷烃的谱线强度要大于异烷烃等同分异构体的谱线强度,表现出了明显的与甲基移动的个数有关的性质.  相似文献   

11.
12.
The frontier molecular orbitals (HOMO and NHOMO) of CF2BrCl molecule have been firstly investigated by (e,2e) electron momentum spectroscopy. The experimental momentum profiles are compared with the theoretical profiles employing Hartree-Fock and density functional theory with 6-31G and 6-311+G(d) basis sets. Both HF and DFT calculations using 6-311+G(d) basis set can well describe the experiment, whereas those calculated using 6-31G basis set largely underestimate the experiment at the low momentum region. Furthermore, orbital electron density images show that HOMO and NHOMO have a mixed character of the bromine and chlorine lone pairs.  相似文献   

13.
    
The outer-valence binding energy spectra of ethanol in the energy range of 9-21 eV are measured by a high-resolution electron momentum spectrometer at an impact energy of 2.5 keV plus the binding energy. The electron momentum distributions for the ionization peaks corresponding to the outer-valence orbitals are obtained by deconvoluting a series of azimuthal angular correlated binding energy spectra. Comparison is made with the theoretical calculations for two conformers, trans and gauche, coexisting in the gas phase of ethanol at the level of B3LYP density functional theory with aug-cc-pVTZ basis sets. It is found that the measured electron momentum distributions for the peaks at 14.5 and 15.2 eV are in good agreement with the theoretical electron momentum distributions for the molecular orbitals of individual conformers (i.e., 8a' of trans and 9a of gauche), but not in accordance with the thermally averaged ones. It demonstrates that the high-resolution electron momentum spectrometer, by inspecting the molecular electronic structure, is a promising technique to identify different conformers in a mixed sample.  相似文献   

14.
The electron momentum profile for inner valence orbitals 2b and 3a of cyclohexene (C6H10) was firstly studied by the binary (e,2e) electron momentum spectroscopy (EMS), at the impact energy of 1200 eV plus binding energy using symmetric non-coplanar kinematics. The complete valence shell binding energy spectrum of C6H10 was also obtained. The experimental momentum profile of the summed orbitals was compared with Hartree Fock (HF) and density functional theory (DFT) methods with various basis sets. The experimental measurement was well described by the HF and DFT calculations except for the low-p region (p<0.25 a.u.). Experimental small “turn-up” effects of momentum profile in the low-p region could be due to the distorted wave effects.  相似文献   

15.
编写了普适性的多键表自洽场程序,该程序能对单电子轨道展开系数和键表系数同时优化,其中单电子轨道的展开空间可任意定义,实际计算建议采用“杂化”轨道形式,即每个单电子轨道只对一个原子的基函数展开。对H2、Li2及HLi采用不同基组进行计算,结果表明用3个键表自洽计算所得能量与MP2结果相近,且我们的计算对键的共价性和离子性分析非常直观。  相似文献   

16.
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.  相似文献   

17.
    
van Lenthe, Broer, and Rashid made comments on our 2009 paper [Song et al., J. Comput. Chem. 2009, 30, 399] by criticizing that we did not properly reference the work by Broer and Nieuwpoort in 1988 [Broer and Nieuwpoort, Theor. Chim. Acta. 1988, 73, 405], and we favorably compared our valence bond self‐consistent field (VBSCF) algorithm with theirs. However, both criticisms are unjustified insignificant. The Broer–Nieuwpoort algorithm, properly cited in our paper, is for the evaluations of matrix elements between determinants of nonorthogonal orbitals. Stating that this algorithm “can be used for an orbital optimization” afterwards [van Lenthe et al., submitted] is not a plausible way to require more credits or even criticize others. While we stand by our statement that our algorithms scales at O(m4) and van Lenthe et al.'s approximate Newton Raphson algorithm scales at O(mN5) (here m and N are the numbers of basis functions and electrons), as we discussed in our original paper, it becomes obvious that any strict comparison among different algorithms is difficult, unproductive, and counteractive. © 2012 Wiley Periodicals, Inc.  相似文献   

18.
本文采用对称非共面(e,2e)的几何条件分别在1200和1600 eV入射电子能量下测量了环戊烯分子的价轨道电子动量分布. 理论上使用简谐近似量子力学和热采样分子动力学的方法计算得到了环戊烯分子的理论价电子动量分布,并与实验结果进行了比较. 结果表明,对于像环戊烯这种柔性的环状分子来说,包括环折叠在内的分子振动运动,对外价层轨道的电子动量分布有显著的影响,尤其是在低动量区域这种影响更加明显. 对于环戊烯的类π*轨道3a'和2a'+3a'来说,其实验电子动量分布与入射电子能量相关表明了扭曲波效应的存在.  相似文献   

19.
The electron momentum spectroscopy of the inner valence orbitals 3a1 and 2b2 of methylene fluoride was studied by electron momentum spectroscopy(EMS). The experiment was performed using a high resolution(ΔE=1.15 eV FWHM,Δp=0. 1 a. u.)(e,2e)EMS spectrometer. The experimental momentum profiles of these two orbitals are compared with those calculated by Hartree-Fork method and Density Functional Theory.  相似文献   

20.
Orbital energy parameters, previously obtained from atomic valence state energies, are used in calculating approximate wave functions for their orbitals. The radial factors of these wave functions are expressed as linear combinations of three Gaussian type orbitals with selected exponents, the coefficients being determined by normalisation and reproduction of the kinetic energy and interelectron repulsion parameters. Wave functions of universal form are obtained for the non-transition elements up to xenon. Each calculated s orbital wave function (except 1s) has a radial node, as is appropriate if there is a p orbital in the same shell with none.  相似文献   

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