强电离放电研究

采用特种工艺,将高绝缘强度、高介电常数的Al2O3制成的电介质薄层覆盖在电极表面,应用窄间隙结构组成介质阻挡放电装置,能够在大气压或高于大气压条件下实现强电离放电,获得的折合电场强度大于400Td,电子平均能量大于10eV,电子密度高于1015/cm3·这足以使等离子体化学反应腔体里大部分的气体分子离解、电离成电子、离子、自由基、激发态原子等活性粒子,实现在原子或原子团簇尺度上重新组合成新物质     

用B-样条函数展开方法研究里德堡原子铯Stark态的能级结构

利用隆样条函数结合原子模型势方法，研究了在静电场作用下里德堡铯原子Stark能级精细结构，得到了与实验符合很好的结果，并分析了能级反交叉产生的原因．     

Attosecond control of electrons emitted from a nanoscale metal tip

Attosecond science is based on steering electrons with the electric field of well controlled femtosecond laser pulses. It has led to the generation of extreme-ultraviolet pulses with a duration of less than 100 attoseconds (ref. 3; 1 as = 10(-18) s), to the measurement of intramolecular dynamics (by diffraction of an electron taken from the molecule under scrutiny) and to ultrafast electron holography. All these effects have been observed with atoms or molecules in the gas phase. Electrons liberated from solids by few-cycle laser pulses are also predicted to show a strong light-phase sensitivity, but only very small effects have been observed. Here we report that the spectra of electrons undergoing photoemission from a nanometre-scale tungsten tip show a dependence on the carrier-envelope phase of the laser, with a current modulation of up to 100 per cent. Depending on the carrier-envelope phase, electrons are emitted either from a single sub-500-attosecond interval of the 6-femtosecond laser pulse, or from two such intervals; the latter case leads to spectral interference. We also show that coherent elastic re-scattering of liberated electrons takes place at the metal surface. Owing to field enhancement at the tip, a simple laser oscillator reaches the peak electric field strengths required for attosecond experiments at 100-megahertz repetition rates, rendering complex amplified laser systems dispensable. Practically, this work represents a simple, extremely sensitive carrier-envelope phase sensor, which could be shrunk in volume to about one cubic centimetre. Our results indicate that the attosecond techniques developed with (and for) atoms and molecules can also be used with solids. In particular, we foresee subfemtosecond, subnanometre probing of collective electron dynamics (such as plasmon polaritons) in solid-state systems ranging in scale from mesoscopic solids to clusters and to single protruding atoms.     

Attosecond real-time observation of electron tunnelling in atoms

Atoms exposed to intense light lose one or more electrons and become ions. In strong fields, the process is predicted to occur via tunnelling through the binding potential that is suppressed by the light field near the peaks of its oscillations. Here we report the real-time observation of this most elementary step in strong-field interactions: light-induced electron tunnelling. The process is found to deplete atomic bound states in sharp steps lasting several hundred attoseconds. This suggests a new technique, attosecond tunnelling, for probing short-lived, transient states of atoms or molecules with high temporal resolution. The utility of attosecond tunnelling is demonstrated by capturing multi-electron excitation (shake-up) and relaxation (cascaded Auger decay) processes with subfemtosecond resolution.     

A simulation study of ionization depletion in the auroral ionosphericF-region caused by strong convection electric field

THe effects of strong convection electric field on the electron density in the auroral ionosphericF-region have been simulated numerically by means of a physical model. It is found that an enhancement of electric field directed west-northward in post-noon or west-southward in pre-noon results in an ionization depletion with its maximum at altitudes 40–50 km higher than that of theF ₂ peak. When the enhanced electric field lasts for 45 min and has a maximum about 32 mV/m, the resulted ionization depletions reach their maximum at the time just ∼10 min behind the time when the convection electric field and ion temperature enhancements reach their maximum. This is consistent well with EISCAT observations. The magnitudes of the percentage ionization depletions and their recovery time are dependent not only on the intensity of the electric field, but also on the diurnal variation phase of the background electron density. Foundation item: Supported by the National Natural Science Foundation of China (49674241, 40074039) and the Research Fund for the Doctoral Program of Higher Education in China Biography: Cai Hong-tao (1976-), male, Ph. D. candidate, research direction: polar ionospheric modeling.     

核极化对K~-原子能级的修正

基于SIC-Xα的较为严格的计算方法,对Κ-Pb原子体系中的Rydberg电子态的交换参数采用自洽场模型,并考虑Rydberg电子与原子实间相互作用的影响.借助此方法计算核极化用以修正C.J.Batty光学模型势下的Κ-Pb能级跃迁,整个计算过程不依赖任何经验参数,结果比经典方法更为精确,为奇异原子的深入分析提供了理论参考.     

Synthesis and structure of Cu5(BTA)6(TTA)4 · 5DMF, a copper-nitrogen cluster containing η Π3-benzotriazolate

The title cluster compound—Cu₅(BTA)₆(TTA)₄·5DMF was prepared using thenyltrifluoroacetone and benzotriazolate ligands. The crystal structure indicates that a tetrahedral array of Cu(1), Cu(2), Cu(3) and Cu(4) ions surrounding a central Cu(5) ion are held together by bridging tridentate BTA^- and terminated by TTA^- bond cap. The three nitrogen atoms of a BTA^- bond three different copper ions to form a η³-benzotriazolate. The central Cu ion has a distorted octahedral structure and the surrounding Cu ions are 5 coordinated forming distorted tetragonal structures. The distances between the surrounding Cu(Ⅱ) ions and the central Cu(Ⅱ) ion are in the range of 0.3561—0.3755 nm and those between the surrounding Cu(Ⅱ) ions are in the range of 0.5785—0.6301 nm.     

考虑碰撞的二维离子引出过程的数值模拟

为研究各因素对原子蒸气激光同位素分离（ＡＶＬＩＳ）中离子引出特性的影响,采用二维流体理论电子平衡模型分析计算了引出过程中外加恒定电磁场和电子温度等因素对离子引出特性（引出时间、碰撞损失率）的影响。粒子间的碰撞主要考虑同位素离子和原子间的共振电荷转移,用碰撞截面来处理。数值计算结果表明,外电场和电子温度对离子引出特性影响较大。外电场强,电子温度高,则引出时间短,碰撞损失亦小。而一定的恒定磁场对引出特性影响很小。     

Formation, structure and properties of GeCn± and Ge2Cn± binary clusters

The binary cluster ions Ge₂C_n⁺/Ge₂C_n^- and GeC_n⁺ have been produced by laser ablation. The parity effect is present in the negative ions Ge₂C_n^-, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge₂C_n⁺. An extensive theoretical investigation on GeCn/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂Cn/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) has been carried out by density functional theory at B3LPY level. The calculation shows that the low-lying states of GeC_n/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂C_n/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IP_ad), elec-tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal-culations are due to the kinetic factor in the formation of Ge₂C_n^±.     

Ionization and dissociation of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> and CH<Subscript>2</Subscript>ICl in femtosecond intense field

With the development of ultrafast laser technique,the femtosecond laser electric field is comparable to themolecular field experienced by valence electrons. In thiscase, the classical quantum mechanical theory, based onperturbation theory, becomes inapplicable. Theoreticalunderstanding of the interaction of molecules with intenselaser radiation is quite difficult. The Coulomb explosionhas been extensively studied[1—10] and explained by somesemiclassical models, such as the above threshold ion…     

拓扑绝缘体量子点中的磁交换相互作用

从理论上研究了拓扑绝缘体量子点中的磁交换相互作用.在拓扑绝缘体量子点中,边缘态电子数可以通过量子点的尺寸和外加电场进行调控.当量子点中掺入单个磁离子并且边缘态填充奇数电子时,电子与单个磁离子之间的交换相互作用达到最大值;而边缘态填充偶数电子时,电子与单个磁离子之间的交换相互作用消失.当量子点中掺入2个磁离子时,电子与Mn离子的sp-d相互作用会出现奇偶振荡行为,Mn离子间的相互作用取决于Mn离子间距和量子点壳层中的电子数,表现出典型的Ruderman-Kittel-Kasuya-Yosida型间接交换机制.工作澄清了拓扑绝缘体量子点壳层结构对其磁性的影响,有助于人们设计基于拓扑绝缘体量子点的自旋电子学或量子信息器件.     

Electronic structure and chemical reaction of Ca deposition on resiore8ular poly（3-hexylthiophene） surfaces

Conjugated polymer, regioregular poly（3-hexylthiophene） （rr-P3HT）, films were prepared by spin-coating the rr-P3HT chloroform solution onto clean silicon wafer surfaces. The chemical re- action and electronic structure of Ca deposition on rr-P3HT surfaces were in situ investigated by synchrotron radiation photoemission spectroscopy （SRPES） and X-ray photoemission spectros- copy （XPS）. Upon Ca deposition, Ca-induced band bending of rr-P3HT is observed. In addition, Ca atoms preferentially react with S atoms of rr-P3HT. No obvious reaction between Ca and C atoms can be found. Through the investigation of the evolution of valence band spectra and secondary electron cut-off of rr-P3HT during the process of Ca deposition, an energy level alignment diagram at the Ca/rr-P3HT interface is derived.     

Synthesis,Structure and Antitumor Activities of [Ni（dien）2][Ni（CN）4] Complex

Ni(II)-dien complex was prepared and characterized by X-ray diffraction. The crystal belongs to triclinic system, space group P-1, with crystallographic parametersa=0.888 13(18) nm,b=0.890 10(18) nm,c=1. 591 8(3) nm, α=77.71(3)°, β=89.12(3)°, γ=61.24(3)°,Z=2. The two dien molecules coordinate to the central Ni atom, the six nitrogen atoms form a distorted octahedron. Preliminary pharmacological tests showed this complex had antitumor activity against HepG₂ and HL-60 cell linesin vitro. Foundation item, Supported by the National Natural Science Foundation of China (29972034) Biography: Li Tao (1976-), male, Ph. D candidate, research direction: ophthalmology and chemicalbiology.     

Manipulation of atoms across a surface at room temperature

Since the realization that the tips of scanning probe microscopes can interact with atoms at surfaces, there has been much interest in the possibility of building or modifying nanostructures or molecules directly from single atoms. Individual large molecules can be positioned on surfaces, and atoms can be transferred controllably between the sample and probe tip. The most complex structures are produced at cryogenic temperatures by sliding atoms across a surface to chosen sites. But there are problems in manipulating atoms laterally at higher temperatures--atoms that are sufficiently well bound to a surface to be stable at higher temperatures require a stronger tip interaction to be moved. This situation differs significantly from the idealized weakly interacting tips of scanning tunnelling or atomic force microscopes. Here we demonstrate that precise positioning of atoms on a copper surface is possible at room temperature. The triggering mechanism for the atomic motion unexpectedly depends on the tunnelling current density, rather than the electric field or proximity of tip and surface.     

Electronic structures and infrared spectra of C120O2, C120OS and C120S2

Electronic structures and infrared spectra of C₁₂₀XY molecules (X, Y=O, S) and some of the corresponding ions are investigated using PM3 semi-empirical molecular orbital calculations with full optimization of geometrical structures. It is found that the energy penalty is about 30–42 kJ/mol due to introducing a double bond in the fivemembered ring except for C₁₂₀O₂ ⁻ and triplet C₁₂₀O₂ ²⁻. It is also found that the structures of neutral molecules and the corresponding ions are almost the same; for instance, the change of bond length is less than 0.001 nm. The change of frontier orbits from oxide to sulfide is little as well. The triplet states of C₁₂₀O₂ ²⁻ and C₁₂₀OS²⁻ are more stable than their singlet states, which means that C₁₂₀O₂ ²⁻ and C₁₂₀OS²⁻ follow the Hund’s rule. The vibration analysis showed that the infrared spectra of neutral C₁₂₀O₂ and C₁₂₀OS molecules are in good agreement with the experimental results. Compared with the neutral molecule, vibration frequencies of triplet C₁₂₀O₂ ²⁻ change little, but the vibration intensities are enhanced obviously.     

Size-reduction of Rydberg collective excited states in cold atomic system

The collective effect of large amounts of atoms exhibit an enhanced interaction between light and atoms. This holds great interest in quantum optics, and quantum information. When a collective excited state of a group of atoms during Rabi oscillation is varying, the oscillation exhibits rich dynamics. Here, we experimentally observe a size-reduction effect of the Rydberg collective state during Rabi oscillation in cold atomic dilute gases. The Rydberg collective state was first created by the Rydberg quantum memory, and we observed a decreased oscillation frequency effect by measuring the time traces of the retrieved light field amplitude, which exhibited chirped characteristics. This is caused by the simultaneous decay to the overall ground state and the overall loss of atoms. The observed oscillations are dependent on the effective Rabi frequency and detuning of the coupling laser, and the dephasing from inhomogeneous broadening. The reported results show the potential prospects of studying the dynamics of the collective effect of a large amount of atoms and manipulating a single-photon wave-packet based on the interaction between light and Rydberg atoms.     

金属串配合物[CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt)结构和自旋过滤性质研究

应用密度泛函理论B3LYP方法对金属串配合物[CoMCo(dpa)4(NCS)2](1:M=Co, 2:M=Ni, 3:M=Pd, 4:M=Pt; dpa=dipyridylamide)的成键性质和自旋过滤效应进行了研究,结果表明:配合物1的基态为二重态,Co36+金属链形成三中心三电子键(2nb1*0);而配合物2~4的基态均为反铁磁耦合单重态(AF态),对应的最低能量高自旋态(HS态)分别为三重态、七重态和七重态,单电子分布在两端Co原子上,[CoMCo]6+链具有三中心四电子键(2nb1*1)。由分子轨道能级图和PDOS图分析得到配合物1~4均具有自旋过滤效应,电子传输通道主要为-自旋nb轨道,与费米能级的距离大小为1234。电场作用下,1~4的高电势端Co2―N4键增长而低电势端Co3―N7键缩短,Co―M平均键长略为缩短,Co―M键增强;电场作用下金属原子的自旋密度和电荷密度变化很小,电磁性质稳定;电场作用下nb轨道分布仍保持沿金属轴方向离域,LUMO-HOMO能隙减小,有利于电子输运。     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

掺氮碳纳米管阵列的制备及其场发射特性

使用结构简单的单温炉设备,以二茂铁为碳源与催化剂,三聚氰胺为氮源在硅基底制备出了碳纳米管阵列。所得的碳纳米管为多壁结构,单根碳纳米管的平均直径为50nm,长度为15μm,有着很好的定向性。透射电子显微镜(TEM)和X射线光电子谱(XPS)分析表明所得的碳纳米管是氮掺杂的。利用场发射显微镜研究了掺氮碳纳米管阵列的平面场发射特性,相应的开启场强为1.60V/μm,场发射图像表明了其有较高的场发射点密度。