有机锡化合物的光电子能谱（XPS）研究（Ⅰ）

有机锡化合物的光电子能谱（ＸＰＳ）研究（Ⅰ）李兴林，张瑞峰（中国科学院长春应用化学研究所，长春１３００２２）傅芳信，李洪玉，朱东升（东北师范大学化学系，长春１３００２４）有机锡化合物的合成和结构研究，特别是在生物活性和催化性能方面日益增多［１～３］。...     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

卟啉酞菁模型化合物光致电子转移研究

本文采用时间相关单光子计数对卟啉酞菁ＴＴＰ－（ＣＨ２）ｎ－Ｐｃ模型化合物的光致电子转移进行了研究，发现激发Ｐｃ时，呈现单指数衰减，ｎ＝４时电子转移速率减小，活化能，重排能增加，电子转移效率下降，电子转移反应△ＧＣＳ与电荷分离活化络合物衰变速率ＫＣＴ，按以下规律：△Ｇ＾（５）ＣＳ〉△＾（３）ＣＳ〉△＾（４）ＣＳ〉△＾（２）ＣＳ，ｋ＾（２）ＣＳ〉ｋ＾（３）ＣＳ〉ｋ＾（４）ＣＳ〉ｋ＾（５）ｃｓ。其△Ｇ＾     

双核金属酞菁类化合物催化脱硫机理研究Ⅲ──M（Ⅱ）Pc－PcM（Ⅱ）的电子结构及M（Ⅱ）与Pc间的键合方式

采用ＩＮＤＯ／Ｓ方法研究了双核金属酞菁类化合物Ｍ（Ⅱ）Ｐｃ－ＰｃＭ（Ⅱ）（Ｍ＝Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ）的电子结构．结果表明当金属离子Ｍ（Ⅱ）与酞菁环键合后，其价电子重新布居，从而导致在Ｍ＝Ｃｒ、Ｍｎ、Ｆｅ、Ｚｎ时中心金属离子从酞菁环得到电子；而当Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ时却是中心金属离子向酞菁环转移电子．键合方式的研究结果表明在Ｍ（Ⅱ）Ｐｃ－ＰｃＭ（Ⅱ）分子中，中心金属离子与酞菁环间存在着σ配键、反馈π键和离域π键三种化学键形成，从而在中心金属离子与酞菁环间产生灵活的“电荷呼吸”作用，构成了双核金属酞菁类化合物氧化还原作用的基础．     

synthesisandCrystalStructureof｛（PPh＿3）AgS＿P（OCH＿2PH）＿2｝＿2

ｓｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ｛（ＰＰｈ＿３）ＡｇＳ＿Ｐ（ＯＣＨ＿２ＰＨ）＿２｝＿２＊／／ＬＯＮＧＤｅ－ｌｉｎｇ，ＸＩＮＸｉｎ－ｑｕａｎ￣（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｏｆＣｏｏｒｄｉｎａｔｉｏｎＣｈｅｍｉｓｔｒ...     

Schiff碱类芳香性金属配合物的合成及XPS研究

用乙二胺（或丙二胺）缩乙酰丙酮Ｓｃｈｉｆｆ碱三齿配体与咪唑（或苯并咪唑）及金属离子Ｍ（Ⅱ）配位，合成了１２种Ｓｃｈｉｆｆ碱类类芳香金属配合物，对这类配合物的Ｘ射线光电子能谱研究结果表明，配位后，金属离子的２ｐ电子结合能降低，配位Ｎ原子的１ｓ电子结合能增大；这类配全哦分子中的电荷移行径是以Ｌ→Ｍ为主，其配位键以σ键为主。     

1,2,5-噻二唑衍生物电子结构的紫外光电子能谱研究

首次报导了１,２,５－噻二唑衍生物３－氯－１,２,５－噻二唑（Ａ）和３,４＝二氯－１,２,５－噻二唑（Ｂ）化合物的紫外光电子能谱（ＵＰＳ）,谱带的指认建筑在对谱带形状、相对强度、实验电离能（ＩＰＳ）的分析以对研究分子Ｇａｕｓｓｉａｎ ９４ＳＴ０－６Ｇ从头计算电离能（－ε１）。化合物Ｂ ＵＰＳ谱带的ＩＰＳ比相应的化合物Ａ的ＩＰＳ均你芝归结为Ｂ分子中两个取代Ｃ１原子上电子的拥挤效应。计算的Ｂ的 有量（     

An SCF－MS－Xα Study of the Electronic Structures of Binuclear and Trinuclear Gold（Ⅰ） Compounds

ＡｎＳＣＦ－ＭＳ－ＸαＳｔｕｄｙｏｆｔｈｅＥｌｅｃｔｒｏｎｉｃＳｔｒｕｃｔｕｒｅｓｏｆＢｉｎｕｃｌｅａｒａｎｄＴｒｉｎｕｃｌｅａｒＧｏｌｄ（Ⅰ）ＣｏｍｐｏｕｎｄｓＧＵＯＣｈｕｎ－ｘｉａｏ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＪｉｌｉｎＵｎｉｖ...     

八—4—（四氢糠氧基）双酞菁钕LB膜的电子吸收光谱和扫描隧道显微镜形貌分析

测定了八－４－（四氢糠氧基）双酞菁钕在亚相水面上的π－Ａ曲线，在石英和高取向热解石墨（ＨＯＰＧ）基底上制备了它的ＬＢ膜，解释了八－４－（四氢糠氧基）双酞菁钕的ＵＶ－Ｖｉｓ谱带．并采用扫描隧道显微镜方法观察了ＬＢ膜的形貌，发现在ＨＯＰＧ上双酞菁钕分子是随机分布并有多聚体形成而在ＨＯＰＧ上修饰一层硬脂酸后可得到均匀有序单分散的双酞菁钕分布．所有结果表明大环分子垂直于基底排列     

The Crystal Structure of Hexamolybdenum Halide NaMo_6X_9C_（l4）（X＝Cl_n＋I_（1－n）） by Solid State Reaction

ＴｈｅＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＨｅｘａｍｏｌｙｂｄｅｎｕｍＨａｌｉｄｅＮａＭｏ_６Ｘ_９Ｃ_（ｌ４）（Ｘ＝Ｃｌ_ｎ＋Ｉ_（１－ｎ））ｂｙＳｏｌｉｄＳｔａｔｅＲｅａｃｔｉｏｎ￥ＧｕｏＧｕｏ－Ｃｏｎｇ；ＺｈｕａｎｇＨｏｎｇ－Ｈｕｉ；ＷａｎｇＭａｎ?..     

pH-induced protonation of lysine in aqueous solution causes chemical shifts in X-ray photoelectron spectroscopy

We demonstrate the applicability of X-ray photoelectron spectroscopy to obtain charge- and site-specific electronic structural information of biomolecules in aqueous solution. Changing the pH of an aqueous solution of lysine from basic to acidic results in nitrogen 1s and carbon 1s chemical shifts to higher binding energies. These shifts are associated with the sequential protonation of the two amino groups, which affects both charge state and hydrogen bonding to the surrounding water molecules. The N1s chemical shift is 2.2 eV, and for carbon atoms directly neighboring a nitrogen the shift for C1s is approximately 0.4 eV. The experimental binding energies agree reasonably with our calculated energies of lysine(aq) for different pH values.     

Pseudoequivalent nitrogen atoms in aqueous imidazole distinguished by chemical shifts in photoelectron spectroscopy

The photoelectron spectra of aqueous imidazole are presented, and the N 1s and C 1s binding energies are assigned aided by density functional theory calculations. The chemical equivalency of the two nitrogens of the cationic form is directly identified by the occurrence of a single N 1s photoelectron peak, which results from the delocalization of the positive charge over the molecule as a consequence of the Cv symmetry of the system. In contrast to NMR measurements, the photoemission process is faster than the rapid proton exchange in the aqueous environment, making the pseudoequivalent nitrogens of the neutral state clearly distinguishable with a N 1s binding energy shift of 1.7 eV.     

XPS C 1s binding energies for fluorocarbon–hydrocarbon microblock copolymers

Fluorocarbon–hydrocarbon microblock copolymers –(CF₂)_n–(CH₂)_m– (n = 4, 6, 8; m = 6, 8, 10) were synthesized. Binding energies of the C 1s and F 1s peaks of these copolymers were measured using x‐ray photoelectron spectroscopy. The binding energy of the C 1s peaks of the carbon atoms of the hydrocarbon segments was set at 285.0 eV as the binding energy reference. Unexpectedly, the binding energy of the C 1s peak corresponding to the CF₂ group of the microblock copolymers was determined to be ～291.4 eV, which is ～0.8 eV lower than that of the CF₂ group of tetrafluoroethylene. Copyright © 2003 John Wiley & Sons, Ltd.     

氮气氛中合成杂氮球烯,碳纳米管及纳米晶体的研究

氮气氛中合成杂氮球烯、碳纳米管及纳米晶体的研究詹梦熊，余荣清，王育煌，杨士姚，程大典，刘朝阳，郑兰荪（厦门大学化学系，厦门，３６１００５）关键词杂氮球烯，碳纳米管，纳米晶体，氮气氛自球烯及碳纳米管常规制备方法问世以来［１，２］，制备方法的改进一直成为...     

Density functional calculation of core‐electron binding energies of isomers of C3H6O2 and C3H5NO

The core‐electron binding energies of six isomers of C₃H₆O₂ and four isomers of C₃H₅NO were calculated by a DFT/uGTS/scaled‐pVTZ approach. An average absolute deviation from experiment of 0.15 eV was found for 14 C, N, and O 1s energies. The results confirm the distinctive nature of the X‐ray photoelectron spectra (XPS) of isomers and support the use of electron spectroscopy complemented by accurate theoretical predictions as a tool for chemical analysis. © 1999 John Wiley & Sons, Inc. Int J Quant Chem 76: 44–50, 2000     

Calibration and applications of the ΔMP2 method for calculating core electron binding energies

We calibrated a method for the evaluation of core electron binding energies, based on the energy differences between the cation and neutral molecule evaluated at the level of M?ller-Plesset perturbation theory. The central feature of the method is the use of a mixed basis set: a large all-electron basis set is used for the atom whose core electron is removed, while the model core potential basis set is employed for all remaining atoms. Calibration was carried out for 55 molecules and 114 binding energies of 1s core electrons for the atoms C, N, O, and F. The average absolute deviation for all the core electron binding energies is 0.163 eV. The method was applied to the calculation of the core electron binding energies of five nucleic acid bases (uracil, adenine, cytosine, guanine, and thymine) and several of their low-energy tautomers.     

碱土金属氧化物和过氧化物的O1s电子结合能测定

通过在谱仪真空中对碱土金属氧化物作原位加热, 使其表面碳酸盐分解, 然后记录其晶格氧的O_(1s)电子结合能. 结果表明测得的MgO, CaO, SrO和BaO 的O_(1s)结合能明显地低于大部分文献报导的数值. 本文测得的碱土金属氧化物的O_(1s)电子结合能与氧原子上的Sanderson电荷分数有合理的相关性. 本文测得的BaO_2的O_(1s)结合能是530.9 eV, 它比文献报导的数值要低.     

Theoretical study on interaction of hydrogen with single-walled boron nitride nanotubes. II. Collision, storage, and adsorption

Collision and adsorption of hydrogen with high incident kinetic energies on a single-walled boron nitride (BN) nanotube have been investigated. Molecular-dynamics (MD) simulations indicate that at incident energies below 14 eV hydrogen bounces off the BN nanotube wall. On the other hand, at incident energies between 14 and 22 eV each hydrogen molecule is dissociated at the exterior wall to form two hydrogen atoms, but only one of them goes through the wall. However, at the incident energies between 23 and 26 eV all of the hydrogen atoms dissociated at the exterior wall are found to be capable of going inside the nanotube and then to recombine to form hydrogen molecules inside the nanotube. Consequently, it is determined that hydrogen should have the incident energy >22 eV to go inside the nanotube. On the other hand, we find that the collisions using the incident energies >26 eV could result in damaging the nanotube structures. In addition our MD simulations find that hydrogen atoms dissociated at the wall cannot bind to either boron or nitrogen atoms in the interior wall of the nanotube.     

ESCA-untersuchungen zur ladungsverteilung in alkylierten thioharnstoffderivaten und verwandten thiocarbonylverbindungen

The S 2p, N 1s and C 1s electron binding energies of some substituted thiourea derivatives, isothiouronium salts, thiazolthiones, 1,3,5-thiadiazin-2-thiones and 1,3,5-thiadiazinium salts have been measured using the X-ray photoelectron spectroscopy (ESCA). From binding energy shifts information concerning the charge distribution on the atoms in the molecules was obtained. The positive charge of the isothiouronium salts was found to concentrate on carbon and nitrogen atoms. The charge of the 1,3,5-thiadiazinium cations was found to be delocalized demonstrating the pseudoaromatic character of the electronic system.     

Doubly charged ion mass spectra: VI—Amines

Doubly charged ion mass spectra of 22 amines (2–10 carbon atoms) were determined using an Hitachi RMU-7L double focusing mass spectrometer. Molecular ions were not observed in the spectra of aliphatic amines. The most intense product ion peaks in the spectra of lower molecular weight amines resulted from hydrogen elimination from the molecular ion; however, as amine molecular weight increased the largest peaks resulted from both hydrogen and heavy atom elimination from the molecular ion. Dominant ions in the doubly charged ion spectra of lower molecular weight aliphatic amines were from reactions of [C_nH₃N]²⁺ (n:=2, 3, 4) type ions. The spectra of higher molecular weight aliphatic amines spanned a wide mass range. Appearance energies for some of the more prominent ions were measured in the range from 25 to 49 eV. A geometry optimized quantum mechanical self-consistent field molecular orbital treatment was used to compute the energies and structural parameters of prominent ions in the doubly charged ion mass spectra.