Multiphoton ionization and dissociation of CH3I at 266 and 355 nm

The mechanisms of multiphoton ionization (MPI) and dissociation of CH3I have been studied using timeof-flight (TOF) mass spectrometer at 266 and 355 nm. MPI mass spectrum at 266 nm consists mostly of fragment ions. This is consistent with a neutral-fragment photoionization mechanism in which rapid one-photon dissociation occurs from the repulsive potential energy surface followed by MPI of neutral photofragments. The observation of parent ions at 355-nm excitation is indicative of parent-ionic ladder mechanism in which the parent ions are produced directly by two-photon excitation resonantly excited to Rydberg C state and then ionized through additional one-photon absorption to produce CH3I+. Fragment ions are produced by dissociation of CH3I+.     

The translational energy distributions for metal atoms and ions produced via visible laser MPD/MPI of group 13 metal alkyls and MPI of aluminum and indium atomic beams

The nascent translational energy distributions of group 13 metal ions produced via multiphoton dissociation and multiphoton ionization (MPD/MPI) of their trimethyl derivatives and via multiphoton ionization of metal atomic beams have been measured using time-of-flight mass-spectroscopy. In all cases the ion production was isotropic and the translational energy distribution was approximately Boltzmann. For ionization of free aluminum and indium atoms translational temperatures of 6K and 4K were measured, corresponding to most probable velocities of 60 and 24 ms^–1. From multiphoton dissociation of trimethylaluminum, trimethylgallium, and trimethylindium, translational temperatures of 1800, 700, and 900 K resulted. These correspond to velocities of 1000, 400, and 350 ms^–1. A photodissociation mechanism involving elimination of ethane followed by dissociation of monomethyl metal intermediates to produce metal atoms is in reasonable agreement with the experimental data. The nascent velocities of metal atoms and ions from the metal alkyl and metal beam sources are used to assess the potential of these sources for microfabrication of metal structures.     

丙酮分子的分质量共振多光子电离光谱及多光子电离—离解机理研究

用多光子电离飞行时间质谱法三光子与丙酮分子３ｄ形态和４ｓ态共振的激光波长区域获得了丙酮分子的共振多光子电离分质量多光子电离（ＭＰＩ）光谱和飞行时间质谱，实验观察到的主要产物是ＣＨ３ＣＯ＾＋和ＣＨ＾＋３，还观察到了少量的Ｃ＾＋，ＣＨ＾＋，ＣＨ＾＋２和ＣＨＯ＾＋，在实验的激光波长范围内未见到母体离子，分质量多光子电离光谱具有相似的光谱结构，几个主要谐峰分别对应着（ｎ０，３ｄ）和（ｎ０，４ｓ）里德堡跃迁     

532 nm激光作用下CH3I分子的多光子电离

利用飞行时间质谱仪在超声射流冷却条件下探讨了532 nm激光作用下CH3I分子的多光子电离(MPI)解离过程和机制,得到了分子的飞行时间质谱,质谱中包含较强的I 、CH3 离子信号和较弱的CH3I 、CHn (n≤2)、C 、H 离子信号.不同激光能量下的质谱信号在排布上相似,但在强度上有差别.在532 nm激光作用下CH3I分子的多光子电离包括两个过程:一是CH3I分子由双光子激发到A带解离,生成I原子和CH3基团,然后再吸收光子实现中性碎片电离;另一通道是CH3I分子由三光子共振激发到里德堡C态,处于激发态的母体分子继续吸收两个光子电离形成母体离子,碎片离子可由母体离子解离形成.     

Effects of inverse bremsstrahlung in laser-induced plasmas from a graphite surface

The kinetic energy of electrons emitted due to laser interaction with a graphite surface was studied with a time-of-flight spectrometer. In addition the yields of carbon atomic and molecular ions were measured as a function of laser pulse energy. Pulse energy thresholds for ion emission are observed to correlate with the observed maximum electron energies. Furthermore, the data suggest that ionic carbon clusters can be dissociated by energetic electrons or photons created in the plasma. We believe that initially photoemitted electrons are accelerated by inverse bremsstrahlung to the energies required for electron impact ionization and dissociation     

乙胺分子的多光子电离过程质谱研究

报道了乙胺分子在４４０～４７５ｎｍ波长范围内多光子电离（ＭＰＩ）质谱（ＭＳ）研究结果。碎片离子主要由母体离子碎裂模式产生。母体离子ＣＨ３ＣＨ２Ｎ＋·Ｈ２由经３ｓ里德堡态的（２＋２）共振多光子电离产生后，大部分发生β键断裂，形成ＣＨ２＝Ｎ＋Ｈ２离子，还有一部分再吸收一个光子，通过Ｃ－Ｈ（ＣＨ２）键的断裂产生了ＣＨ３ＣＨ＝Ｎ＋Ｈ２离子。ＣＨ３ＣＨ＝Ｎ＋Ｈ２和ＣＨ２＝Ｎ＋Ｈ２离子最容易发生的碎裂过程是脱去氢分子，分别产生Ｃ２Ｈ４Ｎ＋（分子式）离子和ＣＨ≡Ｎ＋Ｈ离子。     

四氯乙烯的同步辐射光电离研究

利用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四氯乙烯(C₂Cl₄)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C₂Cl₄的电离势IP(C₂Cl₄) =(9.36±0.05)eV及C₂Cl₄光解离碎片离子C₂Cl₃⁺，C_{关键词： 真空紫外光电离 离子出现势 电离势 四氯乙烯}     

Ar原子序列双光双电离产生光电子角分布的理论计算

基于多组态Dirc-Fock方法和密度矩阵理论,给出了原子序列双光双电离光电子角分布的计算表达式,发展了相应的计算程序.利用该程序对Ar原子3p壳层序列双光双电离过程进行了理论研究,给出了光电离的总截面、磁截面、剩余离子取向以及光电子角分布的各向异性参数与入射光子能量的函数关系.结果显示在光电离截面的Cooper极小位置附近取向参数出现极大值,而光电子角分布的各向异性参数在该位置附近出现极小值.进一步给出了33.94和55.34 eV光子能量下序列双光双电离过程中第一步的Ar原子和第二步的Ar^+离子3p壳层光电子角分布,分析了序列双光双电离光电子角分布与单光电离光电子角分布的差异.将计算结果与文献已有的数据进行了比较,具有很好的一致性.本文的研究结果对揭示光与物质相互作用的非线性动力学机制具有重要的参考价值.     

Dynamics simulation on interaction of intense laser pulses with atomic clusters

Under classical particle dynamics, the interaction process between intense femtosecond laser pulses and icosahedral noble-gas atomic clusters was studied. Our calculated results show that ionization proceeds mainly through tunnel ionization in the combined field from ions, electrons and laser, rather than the electron-impact ionization. With increasing cluster size, the average and maximum kinetic energy of the product ion increases. According to our calculation, the expansion process of the clusters after laser irradiation is dominated by Coulomb explosion and the expansion scale increases with increasing cluster size. The dependence of average kinetic energy and average charge state of the product ions on laser wavelength is also presented and discussed. The dependence of average kinetic energy on the number of atoms inside the cluster was studied and compared with the experimental data. Our results agree with the experimental results reasonably well.     

Dissociation of alkane ionized molecules

The subject of investigation is the fragmentation of variously charged molecular ions arising in col-lisions of several kiloelectronvolt H⁺, He²⁺, and Ar⁶⁺ ions with molecules of the simplest alkanes (from methane to butane). Using the method of time-of-flight mass spectrometry, the formation cross sections of dissociation-induced fragment ions are measured. The dissociation takes place when an incident ion captures an electron from a methane, ethane, or propane molecule. The role of additional ionization of the molecule, which accompanies the electron capture by the incident ion, is elucidated. The kinetic energy spectrum for protons resulting from the fragmentation of multiply charged alkane ions is determined. The most plausible kinetic energies of protons depending on the degree of ionization and molecule size fall into the range 1–25 eV. It is shown that, when the molecule loses several electrons, the kinetic energies of protons are governed by Coulomb interaction between all fragment ions and are determined by their flying apart from the relative spatial arrangement of corresponding atoms in a parent molecule.     

MULTIPHOTON IONIZATION MASS SPECTRA OF n-C3H7I AND i-C3H7I AT 532 nm

Multiphoton Ionization (MP) Mass Spectra of n-C₃H₇I AND i-C₃H₇I are obtained using a time-offlight mass spectrometer at 532 nm. No parentions are observed in MPI of both isomers. N-propyl cation dissociates more extensively than isopropyl cation. The C₂H⁺₅(M/Z=29) ion is observed instead of C₂H⁺₄(M/Z=28) ion in MPI of n-C₃H₇I, in contrast to i-C₃H₇I. It is found that parent molecules are first two-photon resonantly excited to A-band, then go through dissociation. Fragment ions are produced by ionization and dissociation of neutral fragments. We present directly the diss ociation pathways of n-propyl cation according to the results proposed by Levine using maximum entropy formalism. Moreover, those of isopropyl cation are discussed in this paper through branching ratio analyses.     

Mass spectral fragmentation patterns of 1a,3-diaryl-1,1,4, 4-tetrachloro-1a,2,3,4-tetrahydro-1H-azirino

The mass spectrometric behaviour of three 1a,3-diaryl-1,1,4, 4-tetrachloro-1a,2,3,4-tetrahydro-1H-azirino-[2,1-e][1, 6]benzothiazocines has been studied with the aid of mass-analyzed ion kinetic energy spectro--metry and exact mass measurements under electron impact ionization. All compounds show a tendency-to eliminate a neutral substituted/unsubstituted 1,1-dichlorostyrene from the eight-membered thiazocine ring to yield azirino[2,1-c][1, 4]benzothiazine ions, which can then lose a chlorine radical and a sulfur-atom to form azirino[2,1-c][1,4]benzothiazine ions and dihydroquinoline ions. All compounds could also eliminate a chlorine radical plus hydrogen chloride, stepwise or consecutively, to undergo a ring enlargement rearrangement to produce nine-membered 1, 7-benzothiazonine ions. The [M(+) - Cl] ions could undergo a four-membered ring rearrangement to yield 1,5-benzothiazepine ions by loss of 1,1-dichlorostyrene or styrene ions and HCl, and undergo alpha, alpha-cleavage to form benzothiazine ions by loss of arylchlorocyclopropane. The [M(+) - Cl - HCl] ions could further eliminate some atoms, small molecules or molecular fragments to form some abundant fragment ions. Copyright 1999 John Wiley & Sons, Ltd.     

在超声分子束下气相四甲基硅分子的多光子解离与电离

采用超声分子束技术，以飞行时间质谱仪，在４１０～３７１ｎｍ内着重检测了不同波长、不同能量的激光对气相Ｓｉ（ＣＨ３）４分子多光子电离（ＭＰＩ）飞行时间（ＴＯＦ）质谱产物分布的影响。根据实验结果，对Ｓｉ（ＣＨ３）４分子多光子解离电离可能经历的通道和反应机理进行了讨论。     

Predicting secondary ion formation in molecular dynamics simulations of sputtering

We present a model to incorporate the excitation and ionization of sputtered particles into molecular dynamics simulations of ion bombardment-induced collision cascades in metals. The kinetic excitation of the solid is described by electronic friction experienced by all moving particles and electron promotion in close atomic collisions. Transport of the resulting excitation energy is treated by a nonlinear diffusion equation. The resulting space- and time-dependent electron temperature is then introduced into a rate equation model describing the ionization of ejected particles. This way, secondary ion formation is described by assigning an individual ionization probability to every sputtered atom. Averaging over the entire flux, this allows the prediction of measurable quantities like integral or spectral ionization probabilities as well as velocity spectra of secondary ions.     

对乙基苯酚的单色共振双光子电离光谱

对乙基苯酚是构成酪氨酸分子的重要基团,根据其光谱特性可以洞察酪氨酸的光学特性。我们采用超声分子束技术获得了对乙基苯酚的单色共振双光子电离光谱,首次报道了800~1 500cm-1范围的高分辨率激发态振动谱。配合量子化学理论计算分析了各谱对应的振动模式。结果表明取代基越长,分子的激发能越低;取代基的方向对激发能有明显影响;取代基会使苯环平面内的振动能量降低,但取代链的长短对振动能量没有明确影响。研究结果为分子的里德堡态、动力学和零动能光谱的相关研究提供了重要的参考数据。     

Coulomb explosion of large polyatomic molecules assisted by nonadiabatic charge localization

The electron-nuclear dynamics of the Coulomb explosion of a large polyatomic molecule, anthracene, is probed using kinetic energy distributions of produced H+ ions. The kinetic energy release of ejected protons exceeds 30 eV for anthracene exposed to 10(14) W cm(-2), 800 nm pulses of 60 fs duration. We propose a strong-field charge localization model, based on nonadiabatic dynamics of charge distribution in a (multiply) ionized molecule; the charge localization lasts many laser periods and is sustained through successive ionizations of the molecular ion. The model explains quantitatively the dependence of the H+ kinetic energy on the laser intensity. Dissociative ionization of a polyatomic molecule enabled by long-lived charge localization is a new type of electron-nuclear dynamics and is essential for understanding the pathways of molecular or ionic fragmentation in strong fields.     

铝丝阵Z箍缩辐射产生机理初步研究

利用一维非平衡辐射磁流体力学程序研究了铝丝阵内爆过程中的能量转化规律和辐射产生机理.细致讨论了Z箍缩过程中脉冲功率驱动器电磁能馈入等离子体,等离子体动能转化为内能以及通过一系列原子过程电子内能转化为X射线辐射的能量转化机理.结合离子布居信息深入分析了Z箍缩过程中的辐射产生机理.结果表明,在内爆压缩阶段,电离和激发过程占优,线辐射占据总辐射的绝大部分.在滞止时,离子大都处于裸核离化度,连续谱辐射达到峰值.在滞止附近,线辐射出现两个峰值.在膨胀过程中,光电复合过程优于三体复合,线辐射占总辐射的份额逐渐下降.     

Symmetric fragmentation of polyatomic molecular ions in ultrashort intense laser pulses

The intense field-ionization behavior of linear homonuclear polyatomic molecular ions has been numerically investigated for different molecular configurations. The enhanced ionization effect of molecular ions is found as a general feature in a critical bond length range, but the enhancement degree of ionization is bond-selective. The more symmetric the molecular ion stretches, the more enhanced the ionization of the molecular ion. It implies that the symmetric fragmentation of linear molecular ions is most probable at moderate laser intensity. These results are explained in terms of the field-induced over-barrier ionization mechanism.     

Experimental study of the influence of the processes in the ion-beam drift space on beam current measurements

A method is proposed for separate measurements of the current produced by slow charge-exchange ions and that produced by the ions generated due to gas ionization by the beam ions and fast secondary electrons in the beam drift space. The method is based on an analysis of the current distribution over the electrodes of a modified Faraday cup with nonequipotential electrodes and allows one to determine the coefficient of ion-induced electron emission from the ion collector and the charge-exchange cross section of the accelerated ions. The method has been employed to measure the current of an argon ion beam with an ion energy from a few electronvolts to several tens of kiloelectronvolts and to study the processes in the beam drift space at pressures of 0.03–0.15 Pa.     

Time resolved photodissociation of small peptide ions

A new instrument has been constructed whose purpose is to study time-resolved photodissociation (TRPD) of small peptide ions. Laser desorption of neutral peptides is combined with laser photoionization in an ion trap followed by thermalization, laser photodissociation and time of flight mass analysis. Ionization and excitation take place through an aromatic chromophore at the C-terminus of the peptide whereas dissociation produces the immonium ion at the N-terminus. The long-range purpose is to uncover the role of IVR in unimolecular fragmentations of peptide radical cations. One avenue is the determination of microcanonical rate constants at a well-defined internal energy E for a series of peptides possessing the same chromophore, undergoing the same fragmentation but having a variable number of degrees of freedom. This paper demonstrates the feasibility of the method and provides the first attempts at rate measurements for the peptide leucyl tyrosine (LeuTyr). Received 6 January 2002 Published online 13 September 2002