原子核对光电离截面的影响

利用Dirac-Slater相对论平均自洽场理论,研究了不同原子体系光电离截面在不同核模型下的差异.考虑原子核大小时,核的尺寸效应使电子所感受到的有效核电荷减小,并进而影响到电子的概率分布及光电离截面等;对没有考虑原子核大小的点模型,由于不存在核的尺寸效应,出射光电子的波函数有较大相移,从而有可能出现Cooper极小.当入射光子的能量远大于相关电子的电离能时,不同核模型下电子束缚能及平均半径等的差异将相对减小,从而使光电离截面随入射光子能量的变化趋于一致.     

Photoionization cross section and oscillator strength distribution in the near-threshold region of strontium

We present experimentally measured absolute values of the photoionization cross sections from the 5s5p ¹P₁ and 5s5p ³P₁ excited states of strontium at the first ionization threshold as 11.4±1.8 Mb and 10.7±1.7 Mb respectively using saturated absorption technique along with a thermionic diode ion detector in conjunction with a Nd:YAG pumped dye laser system. These threshold photoionization cross sections values have been utilized to determine the oscillator strengths of the 5s5p ¹P₁↦5snd ¹D₂ and 5s5p ³P₁↦5snd ³D₂ Rydberg transitions. The oscillator strength densities in the continuum corresponding to the 5s5p ³P₁ excited state have also been determined by measuring the photoionization cross sections at five ionizing wavelengths above the first ionization threshold. Smooth merging of the discrete f-values into the oscillator strength densities has been observed for the 5s5p ³P₁↦5snd ³D₂ series across the ionization threshold.     

High resolution measurement and MQDT analysis of the 5d<Superscript>9</Superscript> 6s<Superscript>2</Superscript> np,nf (J = 1) autoionizing resonances of mercury

We report new high resolution photoabsorption measurements of the 5d-subshell excitation spectra of mercury using a 3-meter normal incidence spectrograph equipped with a 6000 line/mm holographic grating and synchrotron radiation emitted by the Bonn 2.5 GeV electron accelerator as the background source of continuum. The observed spectra reveal autoionizing resonances attached to the 5d⁹(²D_5/2)6s² and 5d⁹(²D_3/2)6s² parent ion levels of mercury. We have analysed the line shapes of the lower members of the 5d⁹6s² np and nf J = 1 autoionizing resonances using the phase shifted formulation of the MQDT and extracted the interaction parameters.     

Experimental investigation of angular dependence of photon induced L-shell X-ray emission intensity

The angular dependence of emission intensity of L shell X-rays induced by 59.57 keV photons in Pb and U is investigated by measuring the normalized intensities of the resolved L X-ray peaks at different angles varying from 40° to 120°. It is observed that while L _l and L_α X-ray peaks (originating fromJ = 3/2 state) show some anisotropic angular distribution, the emission of L_β and L_γ X-ray peaks is isotropic. The present results contradict the calculations of Co-oper and Zare (1969) that after photoionization of inner shell, the vacancy state has equal population of magnetic substates and the subsequent X-ray emission is isotropic but confirm the predictions of Fluggeet al (1972) that the atomic inner shell vacancies produced after photoionization are aligned and the x-ray emission from the filling of vacancies in state withJ ⩾ 3/2 is anisotropic.     

High-Resolution Threshold Photoelectron Spectroscopy by Vacuum Ultraviolet Laser Velocity-Map-Imaging Method

We have obtained the high-resolution threshold photoelectron (TPE) spectra of chlorobenzene C₆H₅Cl (X¹A₁), propargyl radical C₃H₃ (X²B₁), and allyl radical C₃H₅ (X²A₁) by employing the vacuum ultraviolet (VUV) laser velocity-map-imaging-TPE (VUV-VMI-TPE) method. The photoelectron energy resolution of 1-2 cm^-1 observed for the VUV-VMI-TPE method is comparable to that achieved in VUV laser pulsed-field ionization-photoelectron (VUV-PFI-PE) measurements. Similar to VUV-PFI-PE measurements, the energy resolutions for VUV-VMI-photoelectron (VUV-VMI-PE) and VUV-VMI-TPE measurements are found to depend on the dc electric field F in V/cm used at the photoionization region for electron extraction. The decrease of the ionization thresholds of C₆H₅Cl and C₃H₃ observed as a function of F shows that the Stark shift correction for VUV-VMI-TPE measurements is governed by the formula -3.1√F in cm^-1, which is half of the classical prediction of -6.1√F in cm^-1.} We have also measured the VUV-VMI-PE spectra of C₆H₅Cl and C₃H₅ at VUV energies near their ionization thresholds. The cationic vibrational bands observed in the VUV-VMI-PE measurements were assigned to be the vibrational progression, nv₇⁺ (n=0-3), for C₃H₅⁺. The higher experimental sensitivity and similar energy resolutions achieved in VUV-VMI-TPE compared to VUV-PFI-PE measurements make the VUV-VMI-TPE method an excellent alternative for high-resolution VUV-PFI-PE measurements.     

乙腈＋氯乙烯体系的团簇产生与光电离

利用同步辐射和超声射流技术产生了团簇离子（ＣＨ＿３ＣＮ）＿ｍ（Ｃ＿２Ｈ＿３Ｃｌ）（ｍ≤４，ｎ≤４）及Ｃ２Ｈ３ＣｌＣＮ＋，Ｃ２Ｈ２ＣｌＣＮ＋由（ＣＨ３ＣＮ）（Ｃ２Ｈ３Ｃｌ）＋经团簇内离子。分子反应生成，反应过程中放出能量使Ｈ３Ｃ－ＣＮ键断裂。ａｂｉｎｉｔｉｏ计算表明Ｃ２Ｈ３ＣｌＣＮ＋离子是稳定的。同时测得了它们的电离势．     

利用同步辐射测定NH_3中键的离解能D_0（H_2N—H）及D_0（H_2N~＋－H）

利用同步辐射测定ＮＨ_３中键的离解能Ｄ_０（Ｈ_２Ｎ—Ｈ）及Ｄ_０（Ｈ_２Ｎ~＋－Ｈ）齐飞，盛六四，俞书勤，张允武（中国科学技术大学国家同步辐射实验室，近代化学系，合肥，２３００２６）关键词同步辐射，光电离，氨分子，离解能ＮＨ３分子中Ｎ—Ｈ键离解能的精确测...     

Operating the pulsed discharged detector in both the electron-capture and photoionization modes within the same GC analysis

Summary Since the electron-capture detector (ECD) is highly selective, it is imperative to use a more universal ionization detector in conjunction with the ECD in order to detect non-capturing or weakly capturing compounds. Also in an EC study of weakly or moderately strong electron-capturing compounds, it is necessary to identify the EC peak of the compound by identifying the major component with an ionization detector. In this paper we have shown that the pulsed discharge detector can be interchanged between the EC and the helium ionization modes within 4–6 s. The application of this procedure has been illustrated with a mixture of alkane/alkene chlorocompounds. The interchange between EC and argon photoionization modes has also been investigated. The change from EC to argon photoionization also occurs in 4–6 s but the reverse process requires 9 s.     

Detection limits of thermal conductivity and photoionization detectors in high speed narrow bore CGC

Not only the required input band width and the availability of compatible instrumentation limit the reduction of column diameter but so do the column sample capacity and detector characteristics, such as volume and sensitivity. In this paper the scope and limitations of thermal conductivity and photoionization detection at atmospheric and reduced pressures for capillary gas chromatography are discussed at length. It is shown that the sensitivity of a thermal conductivity detector is inversely proportional to the pressure. Reduction of cell volume and decrease of pressure appear equivalent with respect to minimum detectable amount and peak broadening. This results in femtogram detection limits for column diameters as low as 10 μm. For photoionization detectors the sensitivity did not improve at reduced pressures, so that the effect of reduced pressure and addition of make-up gas on the detection limits is the same. Nevertheless, the applicability of a low volume photoionization detector (40 μl) for capillary columns with a diameter as low as 50 μm will be demonstrated by series coupled PID and FID detectors and illustrated with various applications.