Ar?NO团簇的同步辐射光电离研究

利用国家同步辐射实验室合肥光源的真空紫外同步辐射，使NO分子和Ar原子混合物的超声分子束发生光电离，测量了Ar，NO和异类团簇Ar·NO的光电离效率谱. 在谱中，在与Ar原子的共振线对应的能量区域(11.5—12.0 eV)观察到一个强的类共振结构. 这个结果表明，在异类团簇Ar·NO的内部，稀有气体Ar原子的激发能转移到与它接触的分子NO上，使分子NO发生电离. 关键词： Ar·NO团簇 同步辐射 光电离 能量转移     

Studies of cluster anions C n X− (X=N,P, As,Sb, Bi) produced by laser ablation

A series of cluster anions C _n X^? are produced from laser ablation of appropriate samples, where X is selected as a group-VB element. The recorded mass spectra of these cluster anions display a drastic even/odd alternation on ion intensities: For C _n N^?, only anions with oddn can be observed; For C _n P^? and C _n As^?, cluster anions with evenn are produced but with lower signal intensities; For C _n Sb^?, the signal intensity of clusters does not show even/odd alternation; Finally, for C _n Bi^?, the intensities of cluster anions with evenn are higher than those with oddn. This parity effect can be attributed to the linear structure of the cluster anions, and the parity reversal of C _n X^? from C _n N^? to C _n Bi^? can be explained from the electronegativity decreasing of the heteroatom X as it descends in the group. The Hückel model was applied to account the structural feature of these clusters.     

具有慢磁驰豫和发光性质的基于多胺酚配体的Dy(Ⅲ)和Zn/Ni-Dy(Ⅲ)配合物

合成了4个新的基于多胺酚配体的Dy(Ⅲ)和Zn/Ni-Dy(Ⅲ)配合物:[Dy(CH_3OCH3)L](1),[Dy2(μ-H2O)L2](2),[Zn2DyL2]ClO4·H2O(3)和[Ni2DyL2]ClO4·H2O (4)(H3L=N,N′,N″-三(3,5-二甲基-2-羟基苯酚)-1,4,7-三氮杂环壬烷)。X射线单晶衍射分析表明,配合物1和2分别为单核和双核Dy(Ⅲ)配合物,3和4为M-Dy(Ⅲ)-M三核配合物(M=Zn (3),Ni (4))。磁性测试表明,配合物1和2具有场诱导的慢磁弛豫行为,且2具有多个磁弛豫过程,配合物3和4中没有观察到明显的慢磁弛豫行为。荧光测试表明,配合物1~3具有Dy(Ⅲ)离子典型的窄带特征发射,由于Ni(Ⅱ)离子的荧光猝灭作用,配合物4没有明显的荧光产生。     

二溴甲烷的同步辐射光电离研究

采用５０～２００ｎｍ同步辐射光，对ＣＨ２Ｂｒ２的光电离过程进行了研究，根据测定的母体离子及其碎片离子出现势，得到二溴甲烷的绝热电离势为１０．２３±０．０１ｅＶ，并获得了离子的生成焓，解离能及键能等热力学数据，分析了碎片离子的光解离电离通道。     

Si(CH3)3Cl分子电离电势和化学键能的测定

The photoionization spectroscopy of Si(CH3)3Cl in the range of 50 -130 nm was studied with synchrotron radiation source. The adiabatic ionization potentials of molecule Si(CH3)3Cl and radical Si(CH3)3 are 10.06 ±0.02 eV and 7.00±0.03 eV respectively. In addition, the appearance potentials of Si(CH3)2Cl+, Si(CH3)3+, SiCl+ and SiCH3+ were determined:
AP(Si(CH3)2Cl+) ＝10.49±0.02eV, AP(Si(CH3)3+) ＝ 11.91 ±0.02eV
AP(SiCl+) ＝ 18.64 ±0.06eV, AP(SiCH3+)＝ 18.62 ±0.02eV
From these, some chemical bond energies of Si(CH3)3Cl+ were calculated:
D(Si(CH3)2Cl+ - CH3) ＝0.43 ±0.02eV, D(Si(CH3)3+ - Cl) ＝ 1.85 ± 0.02eV
D(SiCH3+ - (2CH3 ＋ Cl)) ＝ 8.56 ± 0．06eV, D(SiCH3+ - 2CH3) ＝6.71±0．06eV
D(SiCl+ - 3CH3) ＝ 8.58 ± 0.06eV, D(SiCl＋- 2CH3) ＝ 8.15 ±0.06eV
D(SiCH3+- (CH3 ＋ Cl)) ＝8.13 ±0.06eV     

对氨基偶氮苯的同步辐射光电离与光离解

In this paper, the photoionization and photodissociative ionization processes of p-aminoazobenzene (pAAB, C12H11N3) using coincidence technology with vacuum ultraviolet synchrotron radiation (SR) photoionizaton mass spectroscopy are reported. The ionization potential (IP) of this molecule and the appearance potentials (AP) of the important ionic fragments from the SR photodissociative ionization of pAAB have been measured. On the basis of the IP(C12H11N3) and AP measured in this experiment and the IP(C6H5) from the literature, the dissociative energy D 0(C 6H 5-N 2C 6H 4NH 2),D 0(C 6H + 5-N 2C 6H 4NH 2),D 0(C 6H 5-N 2C 6H 4NH + 2),D 0(C 6H 5N 2-C 6H 4NH 2 +) and ionization potential of free radical N 2C 6H 4NH 2 have been evaluated. Based on the results of the mass spectroscopy of pAAB obtained with SR photoionization, the possible channels of photodissociative ionization of pAAB have been analyzed. The processes(molecular ions or the fregmental ions) giving rise to the ions C 6H + 5 and C 6H 6N + need further study.     

Entangled zinc-ditetrazolate frameworks involving in situ ligand synthesis and topological modulation by various secondary N-donor ligands

The introduction of various secondary N-donor ligands into an in situ ditetrazolate-ligand synthesis system of terephthalonitrile, NaN₃ and ZnCl₂ led to the formation of three new entangled frameworks Zn(pdtz)(4,4′-bipy)·3H₂O (1), [Zn(pdtz)(bpp)]₂·3H₂O (2) and Zn(pdtz)_0.5(N₃)(2,2′-bipy) (3) (4,4′-bipy=4,4′-bipyridine; bpp=1,3-bis(4-pyridyl)propane; 2,2′-bipy=2,2′-bipyridine; H₂pdtz=5,5′-1,4-phenylene-ditetrazole). The formation of pdtz²⁻ ligand involves the Sharpless [2+3] cycloaddition reaction between terephthalonitrile and NaN₃ in the presence of Zn²⁺ ion as a Lewis-acid catalyst under hydrothermal conditions. Compound 1 exhibits a fivefold interpenetrating 3D framework based on the diamondoid topology. Compound 2 displays a twofold parallel interpenetrating framework based on the wavelike individual network. Compound 3 possesses a 2D puckered network. These new Zn-ditetrazolate frameworks are highly dependent on the modulation of different secondary N-donor ligands. Their luminescent properties were investigated.     

Anionic passivation layer-assisted trapping of an icosahedral Ag13 kernel in a truncated tetrahedral Ag89 nanocluster

Isolating reductive silver kernel from shell is a challenging task but is quite important to understand the embryonic form during the formation of silver nanoclusters. The intercalation of suitable anionic species may be of benefit for passivating then capturing such highly active kernel. Herein, we successfully isolated a novel silver thiolate nanocluster [Ag13@Ag76 S16(Cyh S)42(p-NH2-Ph As O3)4]3+(SD/Ag89 a, Cyh SH = cyclohexanethiol) that contains a well-isolated icosahedral Ag13 kernel passivated by four Ag S47-tetrahedra and four p-NH2 Ph As O32-piercing from outer Ag72 shell. Of note, this Ag13 kernel is the largest isolable subvalent silver kernel beneath the silver shell with extremely legible core-shell boundary ever before and represents a precise embryonic model formed in the reducing Ag(I) to Ag(0) followed by aggregating to large silver nanoparticles. The reductive role of DMF and the introduction of anionic passivation layer(APL) synergistically modulate the reduction kinetics, facilitating the capture of ultrasmall subvalent silver kernel. SD/Ag89 a emits in near infrared(NIR) region(λem= 800 nm) at low temperature.The synthetic strategy shown in this work opens up new opportunities for precisely capturing and recognizing diverse reductive silver kernels in different systems.     

HFC-152a的同步辐射真空紫外光电离和光解离研究

利用同步辐射真空紫外光，研究了HFC-152a(CH₃CHF₂)的光电离和光解离过程，通过测量各离子的光电离效率曲线，得到了该分子的电离能(11.94±0.04eV)和所有碎片离子的出现势，运用GAUSSIAN-03程序计算了母体和碎片及相应离子的结构、电子态和能量. 结合理论计算的结果，分析了母体离子可能的光电离解离通道及相关通道的解离能. 关键词： 同步辐射 光电离 出现势 HFC-152a     

对硝基甲苯的同步辐射光电离研究

光电离对硝基甲苯（PNT）可获得其电离势及碎片离子的出现势，并由此推断出离子产生的可能通道．目前尚未见到有关PNT光电离研究的报道，仅George等［‘j使用电子轰击电离质谱测得过它的电离势．我们使用同步辐射光电离质谱测得了PNT的电离势和8种碎片离子的出现势，给出了飞行时间（TOF）质谱图，归属了质谱中的主要离子峰，初步分析了光解离电离通道．1实验部分实验装置由阈值光电子一光离子符合（TPEPICO）装置改造而成［’，’］，光电离室上方的四极质谱计由TOF质谱计代替，下方的四极质谱计由盛固体样品的小炉取代．样品蒸…