在ADC(2)水平上通过从头算非绝热动力学方法模拟硝酸甲酯的光解

在ADC(2)水平上通过轨线面跳跃方法模拟了硝酸甲酯的非绝热动力学. 结果证实该体系存在快速的非绝热动力学过程,导致了体系回到电子基态. 当动力学从S₁和S₂电子态开始时,光解产物是CH₃O+NO₂,这个发现与实验研究的结果以及更高精度的XMS-CASPT2水平上模拟出的结果一致. 在ADC(2)水平上,当动力学从S₃态开始时,光解产物依然是CH₃O+NO₂. 该研究表明：ADC(2)方法可用于研究硝酸甲酯在长波下的光解机理,然而无法用于理解其在短波段下的光解动力学. 本文为在ADC(2)水平上处理类似化合物的光诱导过程提供了有价值的信息.     

乙醛光解动力学的离子速度成像

利用时间切片离子速度成像技术在275～321 nm能量范围内重新研究了乙醛自由基通道CH₃+HCO的光解动力学. 通过共振增强多光子电离的方法探测甲基碎片. 对甲基的伞形振动基态和激发态(v₂=0和1)进行了影像探测. 乙醛通过T₁电子态系间窜越到S₁电子态的解离产物具有很高的动能释放和很低的内能激发,碎片的振动能和转动能随激发能量的增加而增加. 乙醛T₁电子态的势垒高度经测量高于基电子态3.881±0.006 eV.     

超高碰撞能23.84 kJ/mol下反应F+D2→DF+D的交叉分子束研究

本文搭建了一套新的实验设备,首次将氢原子里德堡态标记的飞行时间谱技术与激光爆破束源技术相结合,进行超高碰撞能下化学反应的动力学研究. 初步进行了F+D₂→DF+D在超高碰撞能23.84 kJ/mol下的实验研究. 在研究中应用了两种类型束源：一类是通过激光爆破过程产生的高能F原子束源,另一类是通过液氮冷却脉冲阀而产生的D₂束源. 实验中探测了反应产物振动态分辨的微分散射截面. 结果显示,大部分反应产物DF主要呈现侧向和后向散射分布,而产物DF(v''=4)则主要分布在前向. 对前向散射产物DF(v''=4)的动力学来源进行了讨论.     

甲胺水合离子团簇的结构模型及红外光谱研究

本文利用量子化学计算方法，研究了甲胺和水复合离子团簇[(CH₃NH₂)(H₂O)_n]⁺的几何结构、能量和红外光谱，揭示了结构生长模型、氢键作用机制和质子转移机理. 研究结果表明，在[(CH₃NH₂)(H₂O)_n]⁺团簇中，甲胺甲基上的一个氢原子转移到氨基上，形成分子内质子转移的CH₂NH₃⁺离子核心结构模型，水分子作为氢键受体，与质子化氨基NH₃⁺形成氢键. CH₃NH₂⁺离子核心结构模型没有CH₂NH₃⁺离子核心结构模型稳定. 在团簇的红外光谱中，CH振动、自由NH振动、氢键结合的NH振动和OH振动模式在CH₃NH₂⁺和CH₂NH₃⁺两种离子核心结构模型的理论计算红外光谱中明显不同，因此可用于鉴别甲胺水合离子团簇的结构模型，有助于理解甲胺和水复合团簇的氢键网络结构.     

钙钛矿晶体的电荷复合动力学研究

本文利用紫外吸收光谱和稳态荧光光谱技术结合理论模型，研究了钙钛矿材料CH₃NH₃PbI₃晶体在光激发过程中的电荷复合动力学行为，进而获得晶体的扩散长度. 电荷载体的扩散长度是判断光电材料的重要参数. 研究通过合成两种不同缺陷态浓度的CH₃NH₃PbI₃晶体，测量这两种晶体在0.019∽4.268 μJ/cm²的激光激发下的时间分辨荧光光谱，利用动力学模型对光谱进行拟合，可以获得每个晶体的掺杂浓度，空穴浓度以及电荷复合参数. 将这些参数结合已有公式，最终可获得每个晶体的电荷载体的扩散长度.     

CH4-Ne体系的三维从头算势能面与光谱的模拟

本文在从头算CCSD(T)/AVXZ(X=T,Q)水平上计算了CH₄-Ne体系的三维势能面,同时在基组中加入了键函数,并且将基组外推到完全基组极限水平. 通过最小二乘法拟合摩斯长程势能函数形式,获得了三维分析势能面,其中对664个从头算格点的拟合的标准偏差仅为0.042 cm^-1. 随后,采用径向离散变量表象和角度有限基组表象相结合的杂化基函数方法,并基于Lanzcos迭代的方法获得了CH₄-Ne体系的振转能级,所预测的红外光谱与实验值非常吻合. 本文首次给出了CH₄-Ne体系的微波光谱数据. CH₄-Ne体系三维摩斯长程势能面分析的表达式为今后CH₄在Ne团簇动力学性质以及其碰撞诱导吸收光谱的研究中奠定了基础.     

尺寸和微结构效应对软锰矿红外光谱的影响

合成了纳米纤维状的软锰矿β-MnO₂,其研磨后粒子形貌由纳米纤维转变为纳米粒子,相结构并没有转变．纳米纤维状粒子中心锰离子局域环境有轻微改变．当粒子形貌从长纳米纤维变到短纳米纤维再到纳米粒子时,傅里叶转换红外光谱A_2u频率逐渐从514 cm^-1到574 cm^-1再到617 cm^-1．研究发现依据功能团分析无法确定额外的振动波段来源于不同尺寸和形状粒子的A_2u．通过X射线衍射的Rietveld精修和红外光谱,认为两种MnO₆的八面体构型,如4长+2短,4短+2长,在由不同路线合成的软锰矿中都会存在．微结构对软锰矿傅里叶转换红外光谱最大振动频率的影响是显著的．在红外和远红外区域的四个振动波段都做了分类.     

2-溴丁烷在约265 nm光解离的离子速度成像

用离子速度成像结合共振增强多光子电离技术研究了2-溴丁烷分子在264.77和264.86 nm(约265 nm)的光解离动力学．从获得的离子速度图像确定了光解产物Br和Br*碎片的速度分布和角度分布．其速度分布可以由一个窄的高斯分布拟合得到,它对应于沿着C-Br伸缩模式的直接解离．2-溴丁烷在约265nm的光解离中¹Q₁←³Q₀的非绝热跃迁在Br离子碎片的产生中起到非常重要的作用, 确定Br(²P_3/2)的相对量子产额为0.621．通过约265和约234 nm处2-溴丁烷光解的比较发现,各向异性参数和相对量子产率随着波长增加而下降,³Q₀和¹Q₁态势能面交叉几率随着波长增加而降低     

利用离子-中性光解碎片符合成像研究离子光解动力学

本文对最近研制的低温离子阱-离子速度成像谱仪进行升级,实现了探测离子光解反应的离子产物和中性产物速度影像的符合探测. 实验上利用自制的低温圆柱形离子阱对制备的离子样品进行富集和冷却. 从离子阱中引出的离子束准直后进入一组电势切换电极和离子速度聚焦成像系统开展激光光解实验. 利用一组新设计的离子引出、加速和聚焦电场,离子束可以被加速至4500 eV以上,使中性解离产物获得足够的平动能而被位置灵敏的影像探测器直接探测. 本文利用Ar₂⁺离子的355 nm光解反应对升级后的装置进行测试. 结果表明,光解产生的中性Ar原子和Ar⁺离子产物的速度影像分辨率分别为Δv/v≈4.6%和1.5%.     

LaB6在低压强氮气和氦气中的放电特性

 研究了LaB₆在1~10 Pa氮气和氦气中的直流和脉冲放电特性以及放电过程对电极的影响。结果表明，电极直径为5 mm的LaB6氦气放电管在脉冲工作状态下可以长期稳定放电。在脉冲电压为2.2 kV、脉冲宽度10 ms、频率13.3 Hz下，脉冲峰值放电电流超过120 A。氦气放电管在放电过程中，阴极表面有离子的清洗和活化作用，可以使电极的表面逸出功降低，提高放电管的发射能力和稳定性。LaB₆作为气体放电电极具有寿命长、延迟时间短、放电电流大等优点，可用于重复强流脉冲气体放电的高压高速开关器件。     

Formation of cations and anions upon electron interaction with (doped) helium droplets

Superfluid helium droplets have provided a new perspective for studying electron induced chemistry at extremely low temperatures. Helium droplets represent an ideal environment for the formation of novel and exotic agglomerates of atoms and molecules. Mass spectrometry can be used to detect the resulting ions formed upon electron ionization and electron attachment to doped droplets. In the case of electron ionization a helium atom of the droplet is ionized initially and after few resonant charge transfer reactions between helium atoms the charge finally localises on the dopant. An alternative process is Penning ionization of the dopant, where the scattered electron first electronically excites a helium atom on the surface of the droplet. The attachment of a low energy electron leads to formation of an electron bubble inside the droplet which decays by autodetachment or localization on a dopant, if present in the droplet. In the present minireview a general overview about the field of electron scattering with doped helium droplets is given and a presentation of important recent results related to these electron collision studies is given as well.     

Theoretical analysis of structure, thermodynamic properties, and optical properties of Ge-doped amorphous SiO2

Different stable geometric configurations of Ge doped amorphous SiO₂ (a-SiO₂) system, originating from one, two, or three Si atoms in various places of the a-SiO₂ substituted by Ge atoms randomly have been investigated using interatomic potentials in this work. The most stable structures have been identified and corresponding evolutional rules obtained. The structural growth pattern for Ge-doped a-SiO₂ system is that Ge atoms tend to spread far away from each other and keep away from the center. Furthermore, the thermodynamic properties including speci?c heat, Debye temperature, vibrational entropy, and so on are calculated from the structure with 16 Si atoms of the constructed a-SiO₂ cell replaced by Ge atoms and with the biggest Ge-Ge distance. It can be seen that entropy of Ge doped system with larger specific heat is higher than that of the pure system with smaller specific heat. At last, optical properties including optical absorption spectrum and electron energy loss function of nGe-doped a-SiO₂ (n=0-3, 8) system is also obtained.     

COLTRAP: a 22-pole ion trapping machine for spectroscopy at 4 K

Two similar 4 K 22-pole trapping machines have been recently completed in our laboratory. As a first experimental test in one of them, CH ₅ ⁺ and H₃O⁺ ions have been trapped in the presence of helium gas at 3.8 K and the kinetics and temperature dependence of He tagging investigated. A first shell closure with 5 and (3 + 2) attached He atoms, respectively, is observed for both species. Applying IR radiation in the 3 μm region, helium attachment to CH ₅ ⁺ is hindered by exciting CH-stretches of CH ₅ ⁺ prior to attachment. The resulting spectroscopic signal shows that the kinetic temperature of the stored CH ₅ ⁺ ensemble is below 12 K.     

Measured Cd III Stark widths

The Stark FWHM (Full-Width at Half of the Maximal line intensity, W) have been measured for 16 doubly ionized cadmium (Cd III) spectral lines in a pulsed helium discharge in the wavelength interval between 200 nm and 304 nm. The helium discharge was created in the linear low pressure pulsed arc operated at 19 000 K electron temperature and 5.0×¹⁰²² m−3 electron density. The cadmium atoms were sputtered from the cadmium (99.9% purity) cylindrical plates located in the linear part of the discharge tube. The high density of the Cd III ions is boosted by cascade ionization processes via the well populated Cd II energy levels due to the Penning and charge exchange effects. The shapes of the Cd III lines are recorded using a spectrograph (McPherson model 209, 1.33 m focal-length with 2400 grooves/mm holographic grating) and intensified CCD camera (Andor DH740-18F-03) as a high-sensitive detection system. The Stark parameters introduced in this Letter are the first published experimental Cd III Stark widths.     

Electron attachment to doped helium droplets: C60 -, (C60)2 -, and C60D2O- anions

Helium nanodroplets, formed in a supersonic expansion, are doped with C₆₀ in a pickup cell. In some experiments, they are co-doped with water. Electrons are attached to the doped droplets; the yield of anions is recorded as a function of electron energy. The C₆₀ ^- yield extends to much higher energies than in experiments involving isolated, hot fullerenes; we attribute the difference to the low temperature of the neutral precursors and the efficient cooling of the nascent anions by the helium droplet, which quench thermally activated autodetachment. The yields of (C₆₀)₂ ^- and C₆₀D₂O^- anions reveal another important factor, namely depletion of the anion signal by dissociation which is energetically more facile than autodetachment.     

Theoretical investigation of the oxidation pathways of the Cl-initiated reaction of 2-methyl-3-buten-2-ol

The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O₂ have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d,?p) level, and their single-point energies are refined at the CCSD(T)/6-311?+?G(d,?p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311?+?G(d,?p)//MP2(full)/6-311G(d,?p)?+?0.95?×?ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH₃)₂C(OH)CHCH₂Cl (IM1) and (CH₃)₂C(OH)CHClCH₂ (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O₂. The theoretical results show that the major products are CH₂ClCHO and CH₃C(O)CH₃ for the reaction of MBO232?+?Cl in the presence of O₂, which is in good agreement with the experimental finding.     

Spectroscopy of molecules in helium droplets

The work reviewed in the talk explores the possibilities of using molecules immersed in liquid helium as probes to study superfluidity on the microscopic level. For this purpose liquid ⁴He, ³He and mixed ⁴He/³He droplets consisting of 10³–10⁵ atoms have been doped with single molecules or a small defined number of molecules which form clusters in the droplet interior. The dopants were investigated with high-resolution optical spectroscopy. The electronic and rovibrational spectra show unusually sharp spectral lines and unexpected features such as a distinct gap between the zero phonon line and the phonon wing as well as the free rotations of single molecules. Both are not observed in colder nonsuperfluid ³He droplets and therefore are considered to be new microscopic manifestations of superfluidity. Spectroscopic studies of small p-H₂ and o-D₂ clusters surrounding a single chromophore molecule formed in the interior of the He droplets are also reported.     

Catching proteins in liquid helium droplets

An experimental approach is presented that allows for the incorporation of large mass-to-charge ratio selected ions in liquid helium droplets. It is demonstrated that droplets can be efficiently doped with a mass-to-charge ratio selected amino acid as well as with the much bigger m ≈ 12,000 amu protein cytochrome C in selected charge states. The sizes of the ion-doped droplets are determined via electrostatic deflection. Under the experimental conditions employed, the observed droplet sizes are very large and range, depending on the incorporated ion, from 101? helium atoms for protonated phenylalanine to 1012 helium atoms for cytochrome C. As a possible explanation, a simple model based on the size and internal energy dependence of the pickup efficiency is given.     

Kinetics of luminescence induced by sputtering metallic cadmium by a pulsed fast electron beam in helium

Results of an experimental study of the kinetics of luminescence observed when a metallic cadmium foil is bombarded in a helium medium by a 3-ns pulsed beam of 150-keV fast electrons are reported. The foil was irradiated at gas pressures from 76 to 2280 Torr. At a foil temperature of T = 240° C, the de-excitation time of the Beitler levels of the Cd II ion was measured as a function of the buffer gas pressure and the constant of collision quenching of the 5s22D_5/2 level of Cd II by He atoms was determined as k ≈ 3 × 10^-29 cm⁶/s. The experimental data were compared with calculations performed for the gas—vapor mixture in order to find the fraction of excited Cd II ions in the 5s²2D_5/2 state produced directly as a result of sputtering of metallic cadmium by high-energy electrons and by components of the helium plasma. At a helium buffer gas pressure of P ≤ 2.5 atm and a temperature of the cadmium target of T = 240° C, the value of this quantity was found to be α = 0.28 + 0.23P (where P is the helium pressure in atmospheres).     

The origin of disorder in CH 3 HgX (X = Cl, Br and I) crystals investigated by temperature dependent Raman spectroscopy

Methyl-mercury(II) halides CH₃HgX (X = Cl, Br and I) were studied by means of temperature dependent Raman spectroscopy from 10 K to 410 K. In addition to the previously reported soft phonons, new changes in the low frequency spectra were observed at T ≈ 70 K in CH₃HgBr and at T ≈ 100 K in CH₃HgI. The bandwidths of the two internal modes in CH₃HgBr, the CH₃ symmetric stretching band and the C-Hg-Br bending band, rise towards a local maximum at T ≈ 50 K as the temperature is raised from 10 K to 300 K. On the other hand the bandwidths of the two corresponding modes in CH₃HgI crystals monotonously increase with temperature, obeying an Arrhenius law. Besides the three phonon modes present in the Raman spectra of CH₃HgCl at room temperature, the fourth phonon band that has been observed at temperatures below 245 K might correspond to the freezing of methyl librations. The huge bandwidth of the C-Hg-Br bending mode could suggest the presence of additional weak bonding of a mercury atom with bromine atoms from other molecules, thus inducing positional disorder. Received 19 November 1999 and Received in final form 10 November 2000