乙胺和二甲胺分子(n_N,3s)里德堡态共振的多光子电离

MPI质谱研究作为化学分析和研究光物理过程的工具受到广泛的重视[1－4]．REMPI的特征过程是，首先分子吸收。个光子共振激发到中间态，然后处于中间激发态的分子再吸收n个光子激发到电离连续区[5]．REMPI的谱特征可以给出中间态分布的详细信息[6]，利用REMPI过程可研究单光子跃     

二乙胺分子的多光子电离：“梯转换”过程

二乙肤的红外光谱[1]和泛频吸收谱[2]有一定研究，其电子轰击电离[3，4]、场致电离[5]和电子轰击所产生离子的红外多光子及碰撞解离[6]表明，母体离子的碎裂以α键的断裂，从而失去甲基并形成亚胺离子为主．二乙胺分子中N原子与其他原子的构型成锥形，而在母体离子中则成平面结     

呋喃分子多光子电离解离过程的反应通道

1引言呋喃分子在450nm附近的多光子电离实验中[1]，质谱中观察不到母体离子C4H4O＋，主要碎片离子的相对丰度C＋＞C2＋＝CHO＋＝C3H3＋．这些离子的选质量光谱研究表明它们是呋喃分子先吸收3＋1个光子电离为母体离子C4H4O＋，然后C4H4O＋再进一步吸收光子逐步解离产生．陕哺离子的初级解离过程已比较清楚[2－4]，吹响离子能量在1～5eV之间解离通道是：这三个平行解离反应可用RRKM理论来描述[4]．但是陕哺离子在高能量下的解离反应，特别是次级解离过程还不清楚，因此无法确定MPIF实验中观察到小离子碎片产生的机理，为此本文在速…     

碘甲烷通过Ã态和C态的多光子电离

碘甲烷分子与激光相互作用,发生的光解、激发电离等化学或物理过程已由许多人进行过研究.本文报导用多光子电离飞行质谱和光电子能谱技术研究碘甲烷通过(?)态和(?)态的多光子过程的主要实验结果和结论.实验用Nd:YAG 激光器泵浦染料激光器,可调谐的染料(R590)激光经倍频或与YAG 基频1.06μm 混频后分别得到280nm 或366nm 附近的紫外光,能量为0.2—2mJ/脉冲,时间脉     

OCS分子的共振多光子电离光谱

OCS分子的真空紫外吸收光谱早有研究,但有关OCS分子的多光子电离光谱尚未见报导。我们利用可调脉冲激光器,研究了OCS分子的共振多光子电离光谱。首次观察到OCS分子在277—285nm波长范围内的多光子电离光谱。OCS由硫氰酸铵和硫酸反应制取,经多次低温蒸馏纯化。产物通过FT-IR红外光谱和     

含时波包法研究RbI光电子能谱的脉冲延迟效应

利用含时波包方法模拟不同泵浦-探测延迟时间下RbI分子1+3多光子电离时间分辨光电子能谱(TRPES). 模拟过程同时考虑了三光子电离过程和自电离过程. 计算结果表明, 泵浦-探测延迟时间的改变会影响光电子能谱(PES)的形状, 而这种影响实质上是由于强场的存在改变了相关势能面的位置以及势能面之间的交叉所导致的.     

碘代烷烃在532 nm激光作用下多光子电离解离机理

利用５３２ｎｍ的激光对碘代烷烃（碘甲烷、碘乙烷、碘代正丙异丙烷）分子作了多光了电离解离（ＭＰＩＤ）质谱（ＭＳ）研究,在５３２ｎｍ激光作用下,ＣＨ３Ｉ分子吸收５３２ｎｍ激光双光子的能量,进入Ａ带的ＩＡ２态,继续吸收光子上泵浦至电离态形成母体离子ＣＨ３Ｉ,然后再形成碎片离子;而其它几个碘代烷烃吸收双光子的能量进入Ａ带后均形成中性碎片,中性碎片再吸收光子经一系列电离解离形成碎片离子,此外,本文还通过对同     

在超声分子束条件下Mn2(CO)10的多光子电离解离

近年来，人们对具有金属－金属键的Mn2（CO）10分子的光解离电离动力学的研究十分关注．这一方面是由于其独特的分子结构可以获得丰富的光化学及其化学性质方面的信息；另一方面从其结构和光活性之间的关系，有助于了解双核金属有机化合物在催化反应中所起的作用．Leutwyler和Even[1]曾在超声分子来条件下，用脉冲染料激光实现了Mn2（CO）10的多光子电离解离（MPID）过程，获得Mni＋（i＝1，2，3）金属碎片离子．Lichin等人[2]曾用511nm和483nm激光引起Mn2（CO）10的气相多光子解离和电离，测得产物中除了Mn＋，Mn2＋和MnCO＋离子…     

光电子成像方法研究Xe时间分辨多光子电离过程

利用自行研制的离子成像检测器研究了Xe的飞秒时间分辨双色多光子电离过程.Xe的408nm多光子电离对比实验结果表明,该离子成像检测器与相应的进口产品具有相近的光电子能量分辨率.在272nm飞秒激光作用下,3光子电离产生能量为1.57和0.26eV的光电子,分别对应于Xe+的两个自旋态;在408nm飞秒激光作用下,还观察到第一级阈上电离产生的光电子.在双色飞秒时间分辨实验中,随着两束光相对时间的改变,光电子能谱出现了一系列的变化;随着两束光时间重合程度的增加,由双色多光子电离(3+1'或4'+1)产生的光电子信号逐渐加强;在第二束光的作用下,由第一束单色光产生的光电子出现能量红移,第二束光同时也导致中间态布居数减少.这种光电子能谱的红移现象反映了原子体系中激光场诱导有质动力势的时间分辨动态调制过程.     

Kr原子偶宇称自电离Rydberg态共振增强激发光谱研究

利用脉冲直流放电产生Kr原子亚稳态4p^55s[3／2]2和4p^55s’[1／2]0．在29000～40000cm^-1能量范围内,结合飞行时间质谱技术得到Kr原子共振增强激发光谱．光谱分析表明,所有谱线来源于Kr原子4p^55s[3／2]2和4p^55s’[1／2]02个亚稳态吸收单个光子向np’,nf偶宇称自电离Rydberg态的跃迁．观测到许多新的自电离能级,并获得更精确和系统的能级位置和量子亏损值数据．     

OCS+经由A2П←X2П激发的光解离光谱

在超声分子束条件下,由423、420、412.2和408.4nm的电离激光使OCS分子通过[3+1]共振增强多光子电离(REMPI)制备出OCS+(X2Π)离子后,在260-325nm范围内扫描解离激光获得了OCS+离子经由A2Π3/2←X2Π3/2(000)和A2Π1/2←X2Π1/2(000,001)跃迁的分质量光解离谱(母体离子OCS+的凹陷谱和碎片离子S+的增强谱).其中A2Π1/2←X2Π1/2(001)跃迁的光解离谱是首次观察到.由A2Π3/2←X2Π3/2(000)光解离谱得到了A2Π3/2电子态的光谱常数T0=31411.3cm-1,ν1=814.3cm-1;由A2Π1/2←X2Π1/2(000)光解离谱得到了A2Π1/2电子态的光谱常数ν1=816cm-1,ν2=(380.4±2.8)cm-1,ν3=(2052.7±5.1)cm-1,而从A2Π1/2←X2Π1/2(001)光解离谱拟合出的A2Π1/2电子态的ν1(786.4cm-1)稍有不同,表明在A2Π1/2←X2Π1/2(001)跃迁中X2П1/2电子态的C-O键振动(ν3)激发影响了A2Π1/2电子态C-S键的振动(ν1).实验结果表明:在A2Π1/2←X2Π1/2(000,001)跃迁的光解离谱中能够显著观察到属于A2Π电子态的ν2弯曲振动模激发的谱峰,例如A2Π1/2(020,120,021,…),而在A2П3/2(υ1υ2υ3)←X2Π3/2(000)跃迁的光解离谱中几乎没有观察到属于ν2弯曲振动模激发的谱峰.这种弯曲振动激发和A2П电子态的旋轨分裂分量(Ω)的相关性可以通过A2Π电子态的Fermi共振和Renner-Teller效应来解释.     

四甲基硅的多光子电离光谱和质谱

在半导体生产中常用化学气相沉积(CVD)方法制备纯硅.所用的硅化合物原料中,四甲基硅是很重要的一种.与其它种类相比,它不象硅甲烷那样易爆,又不象卤代硅烷那样有腐蚀性,化学性质是比较稳定的.另一方面,它的分子结构Si(CH_3)_4与一般有机金属化合物类似,具有一定代表性.因此研究这个分子的离解和电离过程,以及光物理与光化学性质,在应用和学术方面都是有价值的。     

二乙胺分子的多光子电离："梯转换"过程

The multiphoton ionization (MPI) of diethylamine is first reported in this paper. A time-of-flight mass spectrometer was used in the experiment under collision-free condition. MPI mass spectra were measured in the region of 464 ～486 nm using a dye laser and at double frequency of a Nd:YAG laser. Molecular ion was created through resonance enhanced multiphoton ionization (REMPI) via Rydberg states. Fragment, ion distribution was formed through “ladder switching” process. The experimental demonstration of the process is reported for the first time by the discussion of dependence of ion relative, abundance on laser wavelength and energy. The competition between further up-pumping and fragmentation of Parent ion also exists, and higher laser intensity favors the former.     

以快速预解离态为共振中间态的双色双共振多光子电离光谱

NH_3Ã(~1Ã″_2)是个快速预解离态,寿命约10~(-13)s。本文研究了以这个态为中间共振态的2+1+1双色双共振多光子电离过程。我们首先获得了NH_2和ND_3两分子X→Ã→C′NH_3~+(或ND_3~+)+e跃迁的多光子电离光增, 求出了ND_3C′v_2=0, 1两能级的转动常数,然后通过合理的实验设计, 得到了NH_3分子X→Ã跃迁转动线的增益线型。     

Two-color visible/vacuum ultraviolet photoelectron imaging dynamics of Br2

An experimental two-color photoionization dynamics study of laser-excited Br2 molecules is presented, combining pulsed visible laser excitation and tunable vacuum ultraviolet (VUV) synchrotron radiation with photoelectron imaging. The X 1Sigmag + -B 3Pi0+u transition in Br2 is excited at 527 nm corresponding predominantly to excitation of the v' = 28 vibrational level in the B 3Pi0+u state. Tunable VUV undulator radiation in the energy range of 8.40-10.15 eV is subsequently used to ionize the excited molecules to the X 2Pi32,12 state of the ion, and the ionic ground state is probed by photoelectron imaging. Similar experiments are performed using single-photon synchrotron ionization in the photon energy range of 10.75-12.50 eV without any laser excitation. Photoelectron kinetic energy distributions are extracted from the photoelectron images. In the case of two-color photoionization using resonant excitation of the intermediate B 3Pi0+u state, a broad distribution of photoelectron kinetic energies is observed, and in some cases even a bimodal distribution, which depends on the VUV photon energy. In contrast, for single-photon ionization, a single nearly Gaussian-shaped distribution is observed, which shifts to higher energy with photon energy. Simulated spectra based on Franck-Condon factors for the transitions Br2(X 1Sigmag+, v" = 0)-Br2 +(X 2Pi12,32, v+) and Br2(B 3Pi0+u, v' = 28)-Br2 +(X 2Pi12,32, v+) are generated. Comparison of these calculated spectra with the measured images suggests that the differences in the kinetic energy distributions for the two ionization processes reflect the different extensions of the vibrational wave functions in the v" = 0 electronic ground state (X 1Sigmag+) versus the electronically and vibrationally excited state (B 3Pi0+u, v' = 28).     

He*(23S)/CO2与CS2反应的化学发光

亚稳态原子（或分子）的传能反应，多年来一直受到人们的重视问．Cs。是涉及大气光化学、环境污染的重要分子之一，研究CS。与He”怦S）／CO。的碰撞反应是这些领域共同感兴趣的课题．Masaharu同详细地讨论了He”怦S）／CO与CS。的传能反应·本文在流动余辉装置上，研究了He“怦S）／CO。与CS。传能反应，对实验观察到的电子激发态产物CSt（A、CS（A，a）形成机理进行了讨论．1实验实验装置如图1所示·高纯的He体积分数为99．99％）通过两个装满了分子筛的液氮冷阶进一步提纯，然后由空。。阴极放电产生亚稳态He“炉S）原子·为…     

Photoelectron imaging of atomic iodine following A-band photolysis of CH3I

Photoionization of the iodine atom following methyl iodide A-band photodissociation was studied over the wavelength range of 245.5-261.6 nm by photoelectron imaging technique. Final state-specific speed and angular distributions of the photoelectron were recorded. Two types of the photoelectron resulted from ionizing the I atom from the photodissociation of CH3I were identified: (a) (2+1) REMPI of the ground state I atom, and (b) two-photon excitation of spin-orbit excited I(2P1/2) to autoionizing resonances converging to the 3P1 state of I+. In addition, some weaker signals were attributed to one-photon ionization of I atoms produced in some higher excited states from multiphoton ionization of CH3I followed by dissociation. Analysis of relative branching ratios to different levels of I+ (in case a) revealed that the final ion level distributions are generally dominated by the preservation of the ion-core configuration of the intermediate resonant state. A qualitative interpretation of the electron angular distribution from an autoionization process is also given.     

飞秒脉冲作用下氯丙烯的多光子解离和电离动力学

The dissociation and photoionization dynamics of C₃H₅Cl were studied at 200, 400, and 800 nm with femtosecond laser pulses. The time-of-flight mass spectra, laser power index and photoelectron images were recorded. At short wavelength (200 nm), ionization of the parent molecule was found to be the dominant channel, while other ions were generated by the dissociation of C₃H₅Cl⁺. With the shift to long wavelength (e.g., 800 nm), fragment ions became dominant, and were generated through the multiphoton ionization of neutral fragments after the photodissociation of C₃H₅Cl. These results imply that photodissociation plays a significant role at long wavelength, because neutral fragments are supposed to be generated from the intermediate states reached by 800 nm photons. At 400 nm, the dissociation on the intermediate states is also critical, but is not as high as that at 800 nm. Taken together, our results demonstrate that the dissociation/ionization behaviors of allyl chloride are wavelength-dependent, and reveal the complex dynamics of allyl chloride at 200, 400 and 800 nm.