High-Resolution Infrared-Vacuum Ultraviolet Photoion and Pulsed Field Ionization-Photoelectron Methods for Spectroscopic Studies of Neutrals and Cations

扫描单模红外光参量振荡(IR-OPO)激光器的波长激发待测分子,并用固定波长的真空紫外(VUV)激光器光电离(PI)探测被红外激发的分子,可获得高灵敏度的中性多原子分子的高分辨红外光谱. 这种方法(IR-VUV-PI)基于真空紫外光电离作为探测,可分辨样品中的不同成分,因此适用于对含同位素,自由基,络合物等通常为非纯的样品进行红外光谱研究. 高分辨的IR-VUV-PI谱可实现对分子单一振转态的选择,在选态的基础上进行真空紫外脉冲场电离零动能光电子谱(VUV-PFI-PE)的研究,可得到高分辨振转解析的光电子谱.被研究的分子包括一卤代甲烷(CH3X(X=Br,I)),乙烯(C2H4),丙炔(C3H4)等. 实验表明,采用高分辨的单模红外光参量振荡器代替先前使用的低分辨红外光参量振荡器可显著的提高IR-VUV-PI和IR-VUV-PFI-PE谱的信噪比. 并进一步讨论了采用IR,VUV,分子束三束同轴以提高IR-VUV-PI和IR-VUV-PFI-PE谱灵敏度的方案.     

Application of VUV laser harmonic radiation to the measurement of porous silicon dielectric function

Vacuum ultra-violet (VUV) laser harmonics have been generated in a noble gas jet, which, combined with a standard spectrophotometer, have allowed measurements of the reflectance of porous silicon over a wide energy spectral range from 1 to 16 eV. Porous silicon dielectric function was, then, deduced from reflectance measurements by Kramers–Kronig analysis. Data are found to be in good agreement with those reported in literature, thus showing that laser harmonics represent a new, alternative, and suitable VUV source for optical characterisation of materials such as semiconductors and thin films.     

Photoionization mass spectrometry and modeling studies of the chemistry of fuel-rich dimethyl ether flames

Reaction paths are identified for dimethyl ether (DME) combustion using modeling of new data from fuel-rich DME flat flames. A molecular-beam flame-sampling photoionization mass spectrometer, employing VUV synchrotron radiation, is applied to the measurement of mole fractions for 21 flame species in low-pressure premixed fuel-rich (Φ = 1.2, 1.68) DME/oxygen/argon flat flames. This approach is capable of resolving and identifying isomers and other flame species of near equal masses with ionization thresholds that differ by as little as 0.1 eV. The measurements agree well with flame modeling predictions, using a recently revised high-temperature DME kinetic mechanism, which identify reaction paths quite analogous to alkane combustion. They further reveal the presence of ethyl methyl ether, a molecule previously unobserved in flames and not included in present flame models.     

小分子在真空紫外波段从量子态到量子态的光解离动力学

本文主要描述小分子在真空紫外波段(VUV,6-20 eV)光解离动力学的最新实验和理论研究进展.得益于基于商业化激光器的真空紫外光源技术,以及离子速度成像、高分辨氢原子-里德堡态标记-飞行时间测量和VUV-VUV泵浦-探测等方法的发展,研究人员现在可以对很多小分子在真空紫外波段的光解离动力学进行量子态到量子态层面的测量和研究,本文重点综述H_2(D_2,HD),CO,N_2,NO,O_2,H_2O(D_2O,HOD),CO_2,N_2O以及一些多原子分子在真空紫外波段光解离动力学的最新研究进展.这些小分子在真空紫外波段的光解离在天体化学以及大气化学中有着非常重要的应用.分子吸收一个VUV光子以后,通常会被直接激发到比较高的电子激发态,解离过程会涉及到多个电子态势能面之间的复杂非绝热相互作用.在实验上对解离截面等参数进行从量子态到量子态层面的精细测量对于深入了解这些复杂的势能面之间的相互作用有非常重要的意义.最近建成的大连相干光源是目前世界上唯一一台在真空紫外波段工作的自由电子激光,具有脉冲能量高、扫描范围宽(50～150 nm)等优越的性能,它的建成必将会大大促进小分子真空紫外光解离研究的发展.     

同步辐射真空紫外光电离质谱研究乙烯扩散火焰

本文利用探针取样法结合同步辐射真空紫外光电离和分子束质谱技术研究了常压下的乙烯扩散火焰.通过测量光电离质谱和光电离效率谱分辨了该火焰中大部分的燃烧中间体及产物;通过改变探针取样位置以及半定量计算得到了其中部分燃烧中间体及产物的摩尔分数曲线.实验结果为探索多环芳烃和烟尘在扩散火焰中形成的最初阶段的反应机理提供了依据.     

Determination of the dielectric function of porous silicon by high-order laser-harmonic radiation

Porous-silicon reflectance has been determined over a large energy range, from 1 eV to 16 eV, by combining a NIR/visible/UV spectrometer with a new VUV light source as laser-harmonic radiation. The porous-silicon dielectric function was deduced from reflectance measurements by Kramers–Kronig analysis. We point out that, for the first time, laser harmonics have been applied in the optical characterization of materials as a new and suitable alternative to synchrotron radiation. Received: 9 January 2001 / Accepted: 28 April 2001 / Published online: 20 June 2001     

Photoionization cross section of Xe+ ion in the pure 5p5 2P3/2 ground level

Coupling an ion trap with synchrotron radiation is shown here to be a powerful approach to measure photoionization cross sections on ionic species relaxed in their ground state. The photoionization efficiency curve of Xe+ ions stored in a Fourier transform ion cyclotron resonance ion trap was recorded at ELETTRA in the 20-23 eV photon energy range. Absolute cross sections were derived by comparison of the photoionization yield of Xe+ with measurements from the ASTRID merged-beam experiment. Multiconfiguration Dirac-Fock calculations were performed for the interpretation of these new data.     

Two-color photoionization and photoelectron studies by combining infrared and vacuum ultraviolet

Recent developments of two-color infrared (IR)-vacuum ultraviolet (VUV) and VUV-IR photoionization and photoelectron detection schemes for spectroscopic studies are described. By preparing molecules in selected rovibrational states by IR excitation prior to VUV-photoionization, state-selected and state-to-state photoionization cross sections can be obtained by IR-VUV-photoionization efficiency (IR-VUV-PIE) and IR-VUV-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) measurements, respectively. Rotationally resolved autoionizing Rydberg states converging to excited ionic states, which cannot be observed by single-photon VUV-PIE measurements, can be examined by the IR-VUV-PIE scheme. By monitoring the photoion and the PFI-PE intensities at a fixed VUV energy as a function of IR frequency, the respective IR photoion and IR absorption spectra of the corresponding neutral molecule can be measured. Two-color VUV-IR photo-induced Rydberg ionization (PIRI) experiment, in which high-n Rydberg states are prepared by VUV-photoexcitation followed by IR-induced autoionization, has also been demonstrated. Since the IR-VUV-PIE, IR-VUV-PFI-PE, and VUV-IR-PIRI methods do not require the existence of a bound intermediate electronic state in the UV and are generally applicable to all molecules, the development of these two-color photoionization and photoelectron schemes is expected to significantly enhance the scope of VUV spectroscopy and chemistry.     

氯苯的同步辐射光电离研究

利用真空紫外同步辐射和反射式飞行时间质谱仪对氯苯进行了光电离研究,通过测量各离子的光电离效率(PIE)曲线,得到了氯苯的电离势为(9.11±0.05)eV及两种主要碎片离子C6H+5和C4H+3的出现势分别为(12.96±0.05)和(16.27±0.05)eV.结合有关文献的热力学数据,推导出C6H5Cl+、C6H+5及C4H+3的离子生成焓及一些键的解离能.实验获得了118.0nm同步辐射光电离下氯苯的质谱图.     

Rovibrational-state-selected photoionization of acetylene by the two-color IR+VUV scheme: observation of rotationally resolved Rydberg transitions

We have demonstrated a rovibrational-state-selected photoionization experiment using an IR laser and high-resolution VUV-synchrotron radiation. The VUV photoionization of acetylene [C2H2(Xtilde; (1)Sigma(+)(g);nu(3)=1,J(')=8 or 10)] prepared by IR excitation reveals three strong autoionizing Rydberg series converging to C2H+2(Xtilde; (2)Pi(u);nu(+)(3)=1) with little ion background interference. Rotational transitions resolved for the Rydberg states provide an estimate of approximately 1.8 ps for their lifetimes. This experiment opens the way for state-selective photoionization studies of polyatomic molecules using VUV-synchrotron radiation.     

时间、能量分辨的光电离质谱技术研究气相自由基反应

闪光光解流动管反应器与同步辐射光电离质谱技术两者相结合组成实验平台用于探测气相自由基反应动力学。外触发的脉冲激光光解流动管反应器内的先驱物来产生待反应的自由基;自由基与反应气体发生反应后,由流动管侧壁小孔取样、取样后的混合气体被同步辐射光电离;飞行时间质谱探测光电离产生的离子。同时脉冲信号触发脉冲发生器使其产生一连串的脉冲,间隔40~50μs,此脉冲外触发质谱的采集,连续采集覆盖单次光解反应过程。质谱的时间分辨率为40μs,满足微秒时间内探测反应动力学过程。通过同步辐射光电离反射飞行质谱能直接探测自由基反应产物,并利用光电离效率曲线获得其电离能并区分不同的异构体。实验利用光解产生Cl自由基并与1-丁烯和异丁烯反应,测得反应的加成和消除产物,并获得其加成产物的电离能。     

三氯乙烯的真空紫外同步辐射光电离和光解离

利用真空紫外(VUV)同步辐射光源和反射式飞行时间质谱仪，在超声冷却条件下对三氯乙烯(C₂HCl₃)进行了光电离研究，通过测量各离子的光电离效率(PIE)曲线，得到了C₂HCl₃的电离势P_I(C₂HCl₃)=9.51±0.05eV，以及C₂HCl₃光解离碎片离子的出现势(P_A)：P_{关键词： 同步辐射光电离 电离势 出现势 三氯乙烯}     

Nonstationary heating during VUV photochemical ablation of polymers

According to a previously developed pure photochemical model of VUV laser ablation of polymers, the velocity of ablation front is proportional to surface intensity, and a stationary value of the surface temperature does not depend on laser intensity. Previous estimations show, however, that this stationary surface temperature could be too high to be relevant to the photochemical mechanism. This raises a question of whether the stationary value of the surface temperature can be achieved for a given time shape of light intensity coming to the surface irradiated by a laser pulse of high enough fluence. The intensity time shape is connected not only with the time shape of a laser pulse but also with screening of laser radiation by the plume. This problem is discussed in the present communication. Specifically, it is shown that with a hyperbolic surface intensity time shape, heat diffusion can successfully compete with laser heating decreasing maximum surface temperature compared to its stationary value. The hyperbolic surface laser intensity corresponds to a rectangular laser pulse screened by plume during the photochemical ablation. This allows one to estimate that the photochemical model for a multiple-pulse VUV laser ablation with a high plume extinction coefficient is self-consistent even for a high value of stationary temperature and for high enough laser fluences. PACS 42.62.-b; 44.05.+e; 82.53.-k     

Effective absorption coefficient measurements in PMMA and PTFE by clean ablation process with a coherent VUV source at 125 nm

First measurements of effective absorption coefficient and penetration depth are given here from the ablation of poly-methylmethacrylate (PMMA) and poly-tetrafluoroethylene (PTFE) samples at 125 nm (≈10 eV). The coherent VUV source used which provides smooth, efficient and clean etched areas, is briefly described. Experimental curves of etch depth as a function of the number of laser shots and etch rate as a function of energy density are obtained and compared with previous works performed at 157 nm (F₂ laser) and 193 nm (ArF laser). Experimental results are described with a Beer–Lambert absorption law and discussed. Received: 2 March 1999 / Accepted: 8 March 1999 / Published online: 11 August 1999     

The internal energy of small ammonia clusters in a supersonic beam and after scattering off LiF(100)

The photoionization efficiency (PIE) of neutral ammonia clusters is studied as a function of photon energy. From these curves the internal energies of clusters in the incident supersonic beam and of clusters surviving after scattering off a LiF(100) surface are derived. A supersonic expansion of ammonia seeded in He produces small clusters of various size but with uniform kinetic energy of about 285 meV per monomer molecule. The mass distribution of clusters in the jet and of the scattered particles is measured in a reflecting time-of-flight mass spectrometer by single photon photoionization using vacuum ultraviolet (VUV) laser radiation tunable between and . In the incident beam the internal energies of clusters up to n = 15 do not vary significantly and amount to an average of about . After scattering off LiF(100) the internal energy of clusters up to n = 4 increases with fragment size and amounts to about half a monomer binding energy. Received 18 October 1999 and Received in final form 10 December 1999     

Dipole oscillator strengths for the photoabsorption,photoionization and fragmentation of molecular oxygen

The photoabsorption, photoionization and fragmentation of O₂ have been studied using electron impact coincidence methods to obtain branching ratios and dipole oscillator strengths (cross-sections). The photoabsorption measurements cover the energy range 5–300 eV while the formation of electronic states of O₂⁺ (photoelectron spectroscopy) and the resulting ionic fragmentation (photoionization mass spectrometry) are both measured from close to threshold up to photon energies of 75 eV. The binding energy spectra of O₂ show peaks at 33, 47 and 57 eV in addition to those reported elsewhere in the literature. These peaks are assigned to multiple final ion states arising from photoionization of the inner valence orbitals. Structure in the O₂⁺ electronic state partial oscillator strength curves is in good agreement with recent theoretical work which predicts the existence of several shape resonances. A quantitative picture of the dipole-induced breakdown of O₂ is obtained for the energy range 12–75 eV. The photoionization efficiency is found to be constant above 20 eV.     

Branching ratios and the partial photoionization cross-section for the 3s electron of argon

Binding-energy spectra obtained using the dipole (e, 2e) electron impact coincidence method have been used to derive the 3s/3p cross-section ratios for the photoionization of argon up to 75 eV. The 3s and 3p photoionization branching ratios have been obtained by making use of recently determined double photoionization yields. The partial photoionization cross-section (oscillator strength) for 3s ionization, obtained using the branching ratio and the known total photoionization cross-section, shows the deep minimum ca. 10 eV above threshold which has been predicted by those theoretical calculations which include electron correlation effects. Below 50 eV the cross-section is in excellent agreement with the SRPAE calculation. The results are in close agreement with recent measurements made using synchrotron radiation but are consistently smaller below the minimum and larger at the higher energies.     

VUV-heating of plasma layers and their use as ultrafast switches

We report on new possibilities to generate solid-density plasma at extreme energy density by intense VUV beams. Here we consider 100 fs pulses of 30 eV photons focused to 10¹⁶ and 10¹⁸ W/cm². The temperature evolution in 50 nm thick aluminum foils is discussed on the basis of simulations, performed with the one-dimensional radiation hydrodynamics code MULTI-fs. For 30 eV photons, the foil is shown to switch from transmission to reflection mode on a femto-second time-scale; this is due to the rapid change of the plasma frequency during laser heating which may turn an initially transparent Al-foil into an opaque one. The switching-time depends on the intensity of the laser pulse. Also layered heating structures inside the foil are discussed which occur due to reflection at the rear surface.     

An experimental study of the rich premixed ethylbenzene flame at low pressure

A slightly sooting premixed ethylbenzene flame with an equivalence ratio of 1.90 was investigated at low pressure (4.0 kPa) using molecular-beam mass spectrometry (MBMS) and tunable synchrotron vacuum ultraviolet (VUV) photoionization. Basing on the ionization threshold measurements of photoionization efficiency (PIE) spectra, combustion intermediates up to C₁₉H₁₂ were identified, including a number of radicals and isomeric species. Mole fraction profiles of observed flame species were evaluated from the measurements of burner scan at the photon energies near ionization thresholds. Besides, the flame temperature profile was measured by a Pt/Pt-13%Rh thermocouple. From the intermediate identification and mole fraction measurements, the degradation of ethylbenzene, as well as the formation of some interested polycyclic aromatic hydrocarbons (PAHs), was discussed in detail. It is suggested that the formation of most typical PAHs observed in this work can be related to the H-abstraction/C₂H₂-addition (HACA) mechanism. Furthermore, the high concentration levels of intermediates in this flame is ascribed to the weak C-C bonds in the sidechain of ethylbenzene, which provides a potential explanation of the high sooting tendencies of ethylbenzene and other monocyclic aromatic fuels with complex sidechain structure. This study is anticipated to be constructive for combustion investigations of aromatic fuels, and the discussion is hoped to be helpful for further modeling studies concerning PAHs formation in combustion process.