(CH3I)n(n=1,2,3,4)的同步辐射光电离研究

用VUV同步辐射辐照在连续的超声射流冷却束中产生的（CH₃I)_n（n=1,2，3，4）团簇分子，通过测量其光电离及解离电离产生的各种离子的光电离效率（PIE）曲线，获得了（CH₃I)_n⁺（n=1，2，3，4）的绝热电离势及各种碎片离子的出现势，估算了有关分子的键能．在CH₃I⁺的PIＥ曲线上观察到CH₃I分子的自电离结构，并对其进行了标识，归属为收敛于CH₃I⁺（²E_1/2）态的4组Rydberg系，即ns，npσ，npπ和nd． 关键词：     

CH3I分子的光解离的自旋-轨道从头计算

采用从头计算二阶自旋-轨道多组态准简并微扰理论计算了碘代甲烷CH₃I分子与基态²I⁰_3/2和激发态²I^0*_1/2原子解离极限相关联的势能曲线. 计算了CH₃I分子的吸收谱，分析了CH₃I分子的光解离过程，并估计了激发态碘原子²I^0*_3/2的量子产额. 计算结果表明，该方法可用以解释光解离实验结果. 关键词： 3I分子')" href="#">CH₃I分子 自旋-轨道耦合 量子产额 光解离     

CH3NH3I在制备CH3NH3PbI(3-x)Clx钙钛矿太阳能电池中的作用

利用具有钙钛矿结构的有机-无机杂化卤化物制备的太阳能电池, 由于具有溶液可加工性和高光电转换效率, 受到了广泛关注. 在目前报道的最高光电转换效率的器件中, 采用了CH₃NH₃PbI_(3-x)Cl_x碘氯混合钙钛矿作为吸光层, 据报道在这种材料中光电子的扩散长度可以超过1 μm. 本文综述了在CH₃NH₃PbI_(3-x)Cl_x方面现有的研究工作, 指出了薄膜制备条件的重要性, 并研究了CH₃NH₃I在PbCl₂/CH₃NH₃I热解法制备CH₃NH₃PbI_(3-x)Cl_x吸光层中的作用. 扫描电子显微镜研究表明CH₃NH₃I加入量为PbCl₂的2倍到2.75倍时, CH₃NH₃I加入量的增加可以提高CH₃NH₃PbI_(3-x)Cl_x吸光层的覆盖度和结晶度, CH₃NH₃I加入量进一步增加到3倍时, 形貌变化不大. X射线光电子能谱的数据证实了CH₃NH₃I加入量对覆盖度的影响, 并显示在CH₃NH₃I加入量大于PbCl₂的2.5倍以后, CH₃NH₃PbI_(3-x)Cl_x中氯的掺入量急剧下降. 光电测试表明器件性能随CH₃NH₃I加入量增加而增加, 在CH₃NH₃I/PbCl₂为3/1时达到最高, 加入量略小于3/1对性能影响不大.     

423—475nm的激光作用下呋喃分子的多光子电离离解研究

在波长为423—475nm的激光作用下对呋喃分子的多光子电离离解过程进行了研究.在此实验波段内,呋喃分子主要经历的是(3+1)多光子过程.得到了呋喃分子的共振多光子电离分质量谱以及离子强度与激光强度的关系.对共振多光子电离谱峰进行了里德堡态标识. 关键词：     

800 nm激光作用下碘乙烷的多光子电离解离研究

在800nm飞秒激光作用下对碘乙烷多光子电离解离过程进行了研究,获得了碘乙烷分子的多光子电离飞行时间（MPI-TOF）质谱.光强指数分析表明母体离子主要发生3+3共振增强多光子电离（REMPI）过程.根据部分碎片离子占总离子信号的百分比对激光强度的依赖关系,讨论了碘乙烷的多光子电离解离机制,得出了C₂H₅I分子的多光子电离（MPI）属于母体离子离解阶梯模式.文中分析了母体离子在该波长下主要两条解离通道,其中C-I键的断裂为主要通道.应用高斯03在B3LYP/3-21G基组上计算了两条通道能量的变化,理论进一步验证了实验结果的合理性.     

乙醚团簇的激光电离质谱及从头计算

应用激光多光子电离质谱与超声脉冲分子束技术研究了乙醚团簇，实验中观测到乙醚的碎片离子以及强度较小的(E)H⁺，(E)^＋₂和(E)₂H⁺(E代表CH₃CH₂OCH₂CH₃)，没有发现更大尺寸的团簇离子.结合从头计算理论，在B3LYP/6-311++G(d,p 关键词： 乙醚团簇 偶极-偶极相互作用 从头计算     

丙酮分子的共振增强多光子电离解离过程的实验研究

报道了在280—286.5nm区域内，通过共振增强多光子电离-飞行时间质谱和质量选择光电离激发谱对丙酮分子的光电离和光解离通道进行了研究，并对部分碎片离子的分质量激发谱进行了归属和标识.实验结果表明，在280—286.5nm紫外光波段内，丙酮分子以母体分子的电离通道为主，即首先电离生成母体离子然后母体离子再吸收光子解离生成碎片离子. 关键词： 丙酮 共振增强多光子电离 飞行时间质谱     

利用速度成像技术研究碘乙烷多光子电离解离动力学

卤代烷烃会破坏臭氧层，而碘乙烷（C₂H₅I）是卤代烷烃中重要代表物质之一.采用离子速度成像技术、飞秒激光技术和飞行时间质谱技术，探究了C₂H₅I的多光子电离解离动力学.通过分析C₂H₅I在强场作用下多光子电离解离得到的解离通道、碎片的动能、角度分布和各向异性参数等信息来研究碘乙烷离子（C₂H₅I⁺）C–I键裂解机理.根据飞行时间质谱实验，C₂H₅I在飞秒激光脉冲作用下发生多光子电离解离得到的碎片有C₂H₅⁺，I⁺，CH₂I⁺，C₂H₂⁺，C₂H₃⁺，C₂H₄⁺等.与C–I键相关的碎片为C₂H₅⁺和I⁺，解离机制分别对应于C₂H₅I⁺→C₂H₅⁺+I和C₂H₅I⁺→C₂H₅+I⁺.同时，采用离子速度成像技术研究C₂H₅I⁺的C–I键裂解产生的C₂H₅⁺和I⁺的速度影像，得出两者的速度分布和动能分布，分析结果表明C–I键裂解产生C₂H₅⁺和I⁺的过程都存在高能通道和低能通道.进一步分析解离碎片离子的角度分布发现C₂H₅⁺解离时各向异性参数接近于0，可能对应于慢速的振动预解离过程.I⁺在解离时各向异性参数较高，可能源于排斥势能面上的快速解离过程.最后采用密度泛函理论计算了C₂H₅I分子电离前后构型变化、离子态的能级强度及谐振强度，对C₂H₅I⁺的解离机制做了更进一步的分析和讨论.     

240-250 nm波段氯苯的共振增强多光子电离研究

首次报道了在超声分子束条件下,氯苯分子(C6H5Cl)在240-250 nm紫外激发波段的共振增强多光子电离/飞行时间质谱(REMPI-TOFMS).实验获得母体离子(112C6H5Cl )和一些主要碎片离子的分质量光谱,以及它们在240.5nm和248.6nm两种激发波长下的光强指数.文中对母体离子及主要碎片离子的生成机理进行了探讨,研究表明:该波段范围内,氯苯分子首先吸收一个光子从基态1A1(S0)跃迁至激发态1B2(S1),激发态分子再吸收一个光子而电离,产生母体离子112C6H5Cl ;母体离子直接解离而生成碎片离子77C6H6 .质量更小的碎片离子51C4H3 和27C2H3 则是母体离子进一步吸收光子,然后通过快速的内转换而形成.在该波段范围内,氯苯的最佳检测波长为248.6nm.在该激发波长下,氯苯的探测限能达到到ppb量级.     

二己二硫醚多层膜局域结构的近边x射线吸收精细结构研究

利用多重散射团簇(MSC)方法计算了二己二硫醚［CH₃(CH₂)₅S］₂单分子和多分子硫原子近边x射线吸收精细结构(NEXAFS)谱，给出了二己二硫醚多层膜的局域结构模型. MSC研究显示多层膜中二己二硫醚分子作平行有序排列，彼此相距0.47nm，其横截面呈规则的正方形. 利用离散变分Xα方法计算了二己二硫醚单分子和多分子的电子结构，验证了MSC的计算结果；并阐明了NEXAFS谱中各峰的物理起源. 对多层膜中分子之间的相互作用进行了讨论，发现多层膜的局域结构有分子自组装的特性. 关键词： 3(CH₂)₅S］₂多层膜')" href="#">二己二硫醚［CH₃(CH₂)₅S］₂多层膜 近边x射线吸收精细结构 多重散射团簇方法 离散变分Xα方法     

76500～81120cm~(-1)范围内碘甲烷分子的双光子电离光谱

在离子速度成像的实验装置中,将波长为492~523 nm范围内的激光倍频,以经过倍频的激光作光源,将碘甲烷分子(CH3I)电离,获得了碘甲烷母体分子离子(CH3I+)在76 500~81 120 cm-1范围内的高分辨双光子电离光谱;介绍了CH3I的双光子电离机制,根据Rydberg公式和量子数亏损成功对实验所得到的CH3I+谱中的46个谱峰做了标识,并观察到了CH3I+谱中p,d,f系列的能级分裂。标识结果表明,在CH3I的双光子电离谱中除了可以观察到单光子电离谱的特征,还可以观察到在单光子电离中禁阻的f系列跃迁。     

Adsorption and photodissociation dynamics of methyl iodide on magnesia supported gold nano-particles

Methyl iodide represents a classical model for photodissociation and photoreaction of polyatomic molecules. Here, a new experimental approach is used to study the surface photoreaction dynamics of methyl iodide on magnesia and on magnesia supported gold particles employing pump-probe laser mass spectrometry. The adsorption of methyl iodide at submonolayer coverage on these substrates is investigated via temperature programmed desorption spectroscopy. Two distinct desorption peaks of molecular methyl iodide are identified corresponding to molecules bound to magnesia and more strongly bound to gold, respectively. This permits to selectively investigate the photoreaction of methyl iodide on the gold particles by choosing the appropriate temperature at which all molecules have been desorbed from MgO but not yet from the gold particles. The temperature dependent transient methyl fragment signal reveals the direct photoinduced dissociation dynamics on magnesia, whereas a quenching of the expected dissociation is observed on gold particles.     

A proton magnetic resonance investigation of some weak interactions in solution

The proton chemical shifts of cyclohexane, methyl iodide and iodoform are measured in a number of solvents. A complete calculation of the contribution to the solute proton chemical shift arising from the magnetic anisotropy of cylindrically symmetric solvents is given. Although the formula predicts the direction of the observed shifts, the observed values for non-polar solutes are always much larger than the calculated values. Some possible reasons for this are given and discussed.

The variation of the proton chemical shifts of the polar solutes methyl iodide and iodoform in aliphatic solvents are shown to agree with present theories of these effects. However, in aromatic solvents considerable deviations from the theoretical line are found and these are postulated to arise from solute solvent complexes in which the dipole axis of the solute lies along the hexagonal axis of symmetry of the benzene ring with the protons towards the ring. From the variation of the proton chemical shifts of methyl iodide and iodoform in toluene solution with temperature the following parameters were obtained. For the methyl iodide toluene complex the energy and entropy of formation are 1·3 ± 0·5 kcals/mole and 4·9 ± 0·4 e.u. respectively. For the iodoform toluene complex the corresponding values are 1·6 ± 0·2 kcals/mole and 6·4 ± 0·2 e.u.     

N.M.R. relaxation time studies in liquid methyl iodide

The spin-lattice relaxation times of the various nuclei in methyl iodide, methyl iodide-d ₃, and carbon-13 methyl iodide (¹³C, ¹H, ²D) were measured between 210 and 350 K. The separation of the proton-proton intermolecular relaxation was accomplished by a dilution study in methyl iodide-d ₃; the resulting intermolecular contribution agreed well with the existing theories for this mechanism. It was found that the spin-rotation interaction contributed significantly to the intramolecular relaxation of both the protons and the carbon-13. For both nuclei the separation of the spin-rotation interaction from the intramolecular dipole-dipole interaction was accomplished without making any assumptions about the temperature dependence of the spin-rotation relaxation time. The resulting spin-rotation relaxation times for both carbon-13 and protons offer evidence that the large spin-rotation effects are due to the methyl group reorientation.     

纳秒强光场下碘甲烷的激光电离中高价离子产生研究

利用25纳秒脉冲Nd-YAG 532 nm的激光,在1011 W cm-2的光场强度下,用飞行时间质谱对不同载气条件下碘甲烷的激光电离过程进行了研究.当利用氩作为载气时,除观察到H+,C+,CH+,CH+3,I+,CH3I+等离子外,还观察到很强的C2+,I2+和I3+离子信号.这些高价离子的最可几平动能分别为55.5 eV,9.5 eV和27 eV.质谱峰形的分裂现象以及不同载气的实验结果表明这些高价离子可能来源于碘甲烷团簇的库仑爆炸过程.     

Synthesis of new LC compounds with high optical anisotropy: pentaphenyl derivatives lateral substituted

A new pentaphenyl liquid crystalline (LC) compounds with 2,3-difluorobenzene moiety exhibiting wide nematic range have been prepared. The key stage is the condensation of the corresponding 3-dimethylaminopropanoyl-4-pentyl benzene hydrochloride with substituted methyl benzyl ketone in the presence of base leading to 3,6-disubstituted cyclohexenones. Methylation with methyl magnesium iodide followed by oxidative aromatization gives three-ring bromides, which are used in the Suzuki cross-coupling reaction. Pentaphenyl LC compounds possessing lateral methyl group have moderate melting points, improved solubility, and miscibility with another LC components. The new compounds could be useful in LC compositions with the high optical anisotropy.     

石墨炉原子吸收光谱法测定高温合金中痕量铟

本试验研究了在硫酸介质中用４－甲基戊酮－（２）萃取待测痕量元素铟的碘化物,使之与基体及主量元素分离的最佳试验条件,并对回收率及方法精密度进行了试验,所制定的方法适用于高温合金中铟的分析,试验结果准确可靠。     

碘乙烷在532nm激光作用下多光子电离解离机理

利用５３２ｎｍ的激光对碘乙烷（Ｃ２Ｈ５Ｉ）分子作了多光子电离解离（ＭＰＩＤ）质谱（ＭＳ）研究。Ｃ２Ｈ３Ｉ分子吸收５３２ｎｍ激光双光子的能量激发跃迁至Ａ带后,碎裂成中性碎片Ｉ原子及Ｃ２Ｈ５自由基,中性碎片再吸收光子经一系列电离解离形成碎片离子,分析了不同激光强度及加速电压下的产物离子与总的碳氢离子哟度比值变化,从而更深地揭示了Ｃ２Ｈ５Ｉ分子在５３２ｎｍ激光作用下的ＭＰＩＤ机理。     

Importance of PbI_2 morphology in two-step deposition of CH_3NH_3PbI_3 for high-performance perovskite solar cells

Controlling the morphology of the perovskite film is an effective way to improve the photoelectric conversion efficiency of solar cell devices. In this work, we study the influence of the crystallization condition on PbI_2 morphology and the performances of resulting perovskite solar cells. The PbI_2 morphologies and coverage rates under different formation conditions such as solvent effect, slow crystallization at room temperature and substrate-preheating, are found to be of crucial importance for preparing high-quality perovskite. The generation of loosely packed disk-like PbI_2 film with interpenetrating nanopores promotes the penetration of methyl ammonium iodide(MAI), leading to a better crystallinity of the perovskite film, and a best repeatable power conversion efficiency of 11.59% is achieved when methyl ammonium lead triiodide(CH_3NH_3PbI_3, MAPbI_3) is employed. In addition, an excellent device is also obtained with an efficiency of more than 93% to remain after working for 43 days.     

CuI晶体及其缺陷态电子结构的模拟

利用相对论密度泛函理论和嵌入分子团簇方法,模拟计算了具有闪锌矿结构的γ态CuI晶体及其缺陷态的电子结构。结果显示晶体的本征能级结构:价带顶主要由I5p和Cu3d轨道杂化组成,导带底由Cu4s轨道组成,禁带宽度为3.1eV,该结果与实验相符。在不同缺陷态的计算中,四面体间隙铜缺陷相对其他间隙缺陷更易于在晶体中形成,其中Cu3d→4s跃迁能量为3.2eV,推测与CuI晶体发光密切相关。