激光作用磷化铟所产生的负离子质谱及其分析

以激光蒸发结合超声分子束膨胀,近年来已成为产生与研究原子簇的一种重要手段。在以这一方式产生的Ga_xAs_y的光电离质谱中,发现含奇数个原子的簇离子的信号强度相对较高。最近我们在自制的装置上,于高真空中直接以脉冲激光作用于GaAs、GaP、InP等多种半导体材料,在所记录的负离子质谱中也都观察到类似的奇强偶弱的现象,其中尤以In_xP_y~-最为显著。实验用的激光离子源飞行时间质谱计的构造已有另文详细介绍。该装置通过朝相反方向分别加速正负离子而可同时记录激光等离子体的正负离子质谱。实验采用Nd~(3+):YAG激光器的调Q倍频输出(532nm),聚焦后作用于样品表面的激光功率密度约为10~8W·cm~(-2)。质谱计的加速电压1kV,正负离子的无场漂移长度约1.15m,数据的模数转换速度为2×10~7s~(-1)。实验所用的磷化铟是片状的高纯度半     

C60正负离子的激光引发聚合

自从C_(60)被发现以来,人们普遍认为其具有非常稳定的结构,但我们最近在实验中发现,C_(60)在激光的作用下不仅能形成正负离子,还能进一步聚合成为更大的碳原子簇离子。 1 实验部分 实验在自制仪器上进行。实验中采用高纯C_(60)样品,溅射样品的脉冲激光束波长532nm、脉宽7ns、功率密度10~7W/cm~2。激光产生的正负离子以两台原位飞行时间质谱仪同时检测。实验在10~(-4)Pa真空下进行,实验过程中未引入任何气源。     

激光作用(艹屈)产生的正负离子的相关研究

以高能量密度的脉冲激光束作用于固体样品,可以产生信号强度相近的正负离子.最近我们在一台自制的激光等离子体源飞行时间质谱计上,首次实现了正负离子质谱的同时检测,并通过对稠环芳香烃——(艹屈)的研究,得到了一些有意义的发现.     

富勒烯负离子的自聚行为

C6。可以说是迄今发现的具有最美妙对称性的分子——60个碳原子均位于完全等价的几何位置上，而且由于形成了覆盖整个‘咏’面的大。键，结构非常稳定．最近一系列实验发现，C。。在激光的作用下还能进一步聚合饲．我们在实验中首次发现了C。。在脉冲激光溅射下自聚成的负离子，并对实验记录的质谱作了分析．1实验实验在自制的激光等离子体源飞行时间质谱计问上进行．C。。粉末压紧后以n面胶固定在样品架上．实验所用的激光波长532urn，脉宽7us．会聚后作用于样品的激光功率密度在10’－10‘W·cm－’之间．激光产生的等离子体中的正负离…     

磷原子簇正负离子的激光产生与质谱分析

原子簇的产生与研究,近年来已成为化学与物理学界兴趣的一个焦点。最近我们在自制的装置上,首次观察到各种大小的磷原子簇,并通过对其正负离子质谱的分析,探讨了其可能的构型。实验装置的原理与详细构造已有另文介绍。本实验选择的激光是Nd:YAG激光器的倍频输出(532nm),聚焦后作用于样品的激光功率密度接近10~7W·cm~(-2)。实验的单质磷样品是多次提纯后的红磷。图1所示的磷原子簇的正负离子质谱由两台飞行时间质谱计同时记录,由连续30次采集的数据平均而成。     

铝氧原子簇负离子的激光产生与结构

二元以至多元原子簇(包括铝氧原子簇)的产生与研究是当前十分活跃的领域.最近,我们在自制的装置上,以功率密度达10~8W·cm~(-2)的脉冲激光束(波长532nm)在10_4~-Pa 的真空中溅射AlN 样品时,在实验记录的正负离子质谱中出现的几乎都是铝原子簇离子;而当我们选择α-Al_2O_3为样品时,则观察到了一系列质量分布很广的二元铝氧原子簇负离子,如图1所示.图1的飞行时间质谱是连续100次记录的数据叠加的结果,图中各Al_nO_m~-分别以(n,m)     

四种同分异构的四环稠环芳烃的激光等离子体质谱分析

在常规质谱中,各种同分异构的稠环芳香烃基本上无法分辨。但在本文报道的以近红外脉冲激光所产生的等离子体质谱中,所分析的四个四稠环芳香烃尽管分子量相同,其负离子质谱却有十分明显的差异,显示了这一研究方法的结构鉴别能力。     

激光作用产生的CnH^-、CnF^-、CnF3^-及其结构分析

作者在自制的仪器上, 以脉冲激光(波长532nm, 能量密度10^8W/cm^2)在10^-^4Pa的真空中溅射合适的样品, 产生了一系列CnH^-、CnF^-和CnF3^-, 记录了它们的飞行时间质谱。     

碳原子簇的结构与质谱关联

在自制的仪器上以脉冲激光蒸发和电离单质碳样品,可以产生各种大小的碳原子簇正负离子。这些原子簇的飞行时间质谱可以直接与Hückel规则、Euler定理等相关联。而由此分析得出,随着碳原子簇的增大,它们所经历的各种基本几何构型的转化。     

激光产生的碳原子簇负离子及其质谱研究(II)

近年来,尽管碳原子簇的合成与研究已成为非常热门的课题,但是对其负离子的研究却相对冷落了一些.两年多前,我们以激光在高真空中直接轰击单质碳样品的方式,产生了n≤441的C_n~-并通过对其质谱的分析确定了它们从链状至环状构型的转化.最近,我们又以同样方式产生了成簇原子数高于100的碳原子簇负离子,记录了它们的飞行时间质谱. 本实验选用的样品是光谱纯的碳粉,直接压入样品托座中的小坑.仪器的构造已有另文详细介绍,实验时仪器的主要工作参数与参考文献[1] 中描述的基本相同,只是激光束     

Face-to-face C6F5-[60]fullerene interaction for ordering fullerene molecules and application to thin-film organic photovoltaics

Treatment of [60]fullerene with potassium methylnaphthalenide and excess C(6)F(5)CH(2)Br afforded 1,4-bis(pentafluorobenzyl)[60]fullerene, the study of which showed that there is a face-to-face interaction between [60]fullerene and a perfluoro aromatic ring, allowing the molecule to be utilized for high-performance organic photovoltaic devices.     

Hydroxyfullerene as a novel coating for solid-phase microextraction fiber with sol-gel technology

Hydroxyfullerene (fullerol) as a novel coating for solid-phase microextraction (SPME) fiber was first prepared by a sol-gel technology. The coating procedure involving sol solution composition and conditioning process was presented. A fullerene polysiloxane surface-bonded porous coating on the fused-silica fiber surface was obtained and confirmed by IR spectra and scanning electron microscopy. The coating has stable performance at high temperature (even to 360 degrees C) and solvents (organic and inorganic) because of the properties of fullerene and the chemical binding between the coating and the fiber surface. The extraction properties of the new coatings to less volatile organic compounds, such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons and polar aromatic amines were investigated using headspace SPME coupled with GC-electron-capture detection and GC-flame ionization detection. In addition, compared with commercial SPME stationary phases, the new coatings showed higher sensitivity, faster velocities of mass transfer for aromatic compound, and possessed planarity molecular recognition for PCBs. Moreover, this fiber was firm, inexpensive, durable and can be prepared simply. The fiber-to-fiber reproducibility was very good.     

Synthesis and characteristics of [60]fullerene polysiloxane stationary phase for capillary gas chromatography

A new type of fullerene-containing polysiloxane was synthesized by reacting [60]fullerene with azidopropyl polysiloxane directly. The polysiloxanes have been used successfully as stationary phases for capillary gas chromatography. They displayed high column efficiency, wide operational temperature and high thermostability, and exhibited unique selectivity for many organic substances, such as alkanes, alcohols, ketones and aromatic compounds. The stationary phase was especially suitable for separation of high boiling-point compounds like polycyclic aromatic hydrocarbons and phthalic esters, etc. It was also found that some alcoholic or aromatic positional isomers could be well separated on the column. The influence of the fullerene content on the separation was also investigated.     

Effect of nature of organic solvent on the absorption spectrum of C60 fullerene

Absorption spectrums of C₆₀ fullerene in 10 various organic solvents in the range of 300–620 nm was studied. In all the solvents the C₆₀ fullerene has four absorption maxima in the range under study. When an aromatic solvent has an ionization potential of 8.1 eV or lower a new additional absorption band appears in the absorption spectrum of C₆₀ fullerene, caused by the formation of a charge-transfer complex (CTC) of the solvent and C₆₀ fullerene.     

A step toward direct fullerene synthesis: C60 fullerene precursors with fluorine in key positions

Several fluorine containing polycyclic aromatic hydrocarbons with exact carbon atom topology of the C₆₀ fullerene have been synthesized. Different numbers of fluorine atoms were introduced in the key positions, as needed for an efficient intramolecular condensation to the fullerene molecule. The polycyclic aromatic compounds obtained represent attractive precursors for rational, high-yield fullerene synthesis by flash vacuum pyrolysis.     

Fullerenes from kerogen by laser ablation fourier transform ion cyclotron resonance mass spectrometry

Raw oil shale, kerogen (demineralized shale) and carbonaceous residues from kerogen pyrolysis in the range 350–700°C (at 50°C intervals) were studied by laser ablation Fourier transform ion cyclotron resonance mass spectrometry using the fundamental frequency of Nd: YAG laser (1064 nm). Normally, pyrolysis of the raw materials produces oil and the resulting residues have decreased hydrogen to carbon ratios and exhibit relative increases in aromatic carbons. Raw shale and kerogen give positive-ion spectra with mainly protonated species of m/z 100–400. Laser ablation positive-ion mass spectra of the pyrolysis products of the kerogen show the presence of C₆₀, C₇₀ and other fullerene ions with a distribution of higher mass fullerene ions up to m/z 4000. Using high laser powers (100–3000 MW cm^?2), the residue from pyrolysis at 350°C initially did not produce any fullerene ions (apart from traces of C₆₀ and C₇₀), but after continued ablation a cavity was formed in the target and a wide distribution of fullerene ions was obtained with subsequent laser pulses. Residues obtained from the pyrolysis of kerogen at 400–500°C produced fullerene ions at both low (4–200 kW cm^?2) and high laser powers. The 550°C pyrolysis residue gave only small amounts of C₆₀ and C₇₀ positive ions at low laser power whereas residues from the pyrolysis of kerogen above 550°C did not give fullerene ions over a wide range of laser powers. It is proposed from the above results that the changes in the aromatic nature of the kerogen residues with increasing pyrolysis temperature are directly related to the ease of fullerene formation. This is possibly due to the formation of large polycyclic aromatic systems at pyrolysis temperatures above 400°C, formed in the residues. It should be noted that the shale samples (raw or pyrolysed) did not generate fullerene ions under any of the conditions employed in these experiments.     

An analysis of the structure of fullerene C70 by quantum-chemical methods

Hartree-Fock and density functional theory calculations showed that the B, C, D, and E fullerene C₇₀ cycles were not coplanar. The interrelation between acoplanarity and pyramidality of atoms was studied. The bond lengths, valence and torsion angles, and charges and chemical shifts of fullerene C₇₀ atoms were jointly analyzed. Most attention was given to the acoplanarity of hexagons E in the aromatic belt.     

Photoreactions between [60]fullerene and various aromatic tertiary amines

The photoreactions of [60]fullerene with aromatic tertiary amines such as N,N-dimethylaniline and N,N-dimethyl-1-naphthylamine gave two or three types of [60]fullerene adducts. The reaction efficiency in the series of p-substituted N,N-dimethylanilines remarkably increased with increasing electron-donating properties of aromatic tertiary amines employed.     

Surface-induced enantiomorphic crystallization of achiral fullerene derivatives in thin films

The chirality of organic semiconductors is important for various applications in optoelectronics and spintronics. Here, we propose a new strategy to induce structural chirality in achiral organic semiconductors in thin films. Enantiomeric fullerene derivatives (S)-pSi and (R)-pSi, which have oligo(dimethylsiloxane) as a low-surface-energy moiety, were synthesized and used as surface-segregated monolayers (SSMs) in spin-coated films of several achiral fullerene derivatives. Upon thermal annealing, the presence of the chiral SSMs led to the crystallization of the fullerenes in the films as an SSM-induced crystal phase at lower temperatures. The crystallized films showed circular dichroism ascribed to the fullerene absorption, the sign and the intensity of which depended on the handedness of the SSM molecules and the film thickness, respectively. These results indicate that the achiral fullerene derivatives in the films were induced by the SSMs to crystallize into enantiomorphic crystals. Our approach to inducing chirality in organic thin films is compatible with many device applications.

Chiral induction: surface-segregated monolayers of chiral molecules induce the enantiomorphic crystallization of achiral fullerene derivatives in thin films.     

Electrophoresis of electrostatically assembled fullerene-porphyrin conjugates

The formation of electrostatically coupled assemblies of a series of anionic dendritic fullerene derivatives and cationic porphyrins in buffered aqueous media was studied with gel electrophoresis. Of central interest in these investigations was the variation of the amount of charge carried by the molecules, their size, shape and self-aggregation. Ferric cytochrome c 1 and the more rigid zinc porphyrin served as octacationic species. The two new anionic fullerene derivates 3 and 6 were synthesized. The formation of electrostatic complexes of the fullerene polyelectrolytes 3 and 4 with 1and 2 was clearly evident in the gel electrophoresis experiment. Compounds and showed a similar behaviour towards 2. The electrophoresis experiments confirmed previous results obtained with other techniques on a qualitative level and gave new insights into aggregation phenomena.