锕系元素基态与激发态性质的量子拓扑化学

在基态原子价壳层电子隐核图的基础上,将拓扑理论和量子化学方法相结合,引入价电子的主量子数、角量子数、自旋磁量子数以及价电子的轨道能量等结构参数,得到一个新的量子拓扑指数Ym.利用线性回归方法分别建立了锕系元素16种基态与激发态性质的定量结构-性质关系（QSPR）模型,采用留一法和Jackknife检验相结合的方法,对定量结构-性质相关模型的稳定性和预测能力进行检验.研究结果表明,用新的量子拓扑指数Ym能较好地表征锕系元素的分子结构信息,且所建模型具有良好的稳定性和预测能力.     

Controlled properties of perovskite oxide films by engineering oxygen octahedral rotation

Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.     

Temperature-induced valence transition and associated lattice collapse in samarium fulleride

The different degrees of freedom of a given system are usually independent of each other but can in some materials be strongly coupled, giving rise to phase equilibria sensitively susceptible to external perturbations. Such systems often exhibit unusual physical properties that are difficult to treat theoretically, as exemplified by strongly correlated electron systems such as intermediate-valence rare-earth heavy fermions and Kondo insulators, colossal magnetoresistive manganites and high-transition temperature (high-T(c)) copper oxide superconductors. Metal fulleride salts-metal intercalation compounds of C60--and materials based on rare-earth metals also exhibit strong electronic correlations. Rare-earth fullerides thus constitute a particularly intriguing system--they contain highly correlated cation (rare-earth) and anion (C60) sublattices. Here we show, using high-resolution synchrotron X-ray diffraction and magnetic susceptibility measurements, that cooling the rare-earth fulleride Sm2.75C60 induces an isosymmetric phase transition near 32 K, accompanied by a dramatic isotropic volume increase and a samarium valence transition from (2 + epsilon) + to nearly 2 +. The negative thermal expansion--heating from 4.2 to 32 K leads to contraction rather than expansion--occurs at a rate about 40 times larger than in ternary metal oxides typically exhibiting such behaviour. We attribute the large negative thermal expansion, unprecedented in fullerene or other molecular systems, to a quasi-continuous valence transition from Sm(2+) towards the smaller Sm((2+epsilon)+), analogous to the valence or configuration transitions encountered in intermediate-valence Kondo insulators like SmS (ref. 3).     

Plutonium-based superconductivity with a transition temperature above 18 K

Plutonium is a metal of both technological relevance and fundamental scientific interest. Nevertheless, the electronic structure of plutonium, which directly influences its metallurgical properties, is poorly understood. For example, plutonium's 5f electrons are poised on the border between localized and itinerant, and their theoretical treatment pushes the limits of current electronic structure calculations. Here we extend the range of complexity exhibited by plutonium with the discovery of superconductivity in PuCoGa5. We argue that the observed superconductivity results directly from plutonium's anomalous electronic properties and as such serves as a bridge between two classes of spin-fluctuation-mediated superconductors: the known heavy-fermion superconductors and the high-T(c) copper oxides. We suggest that the mechanism of superconductivity is unconventional; seen in that context, the fact that the transition temperature, T(c) approximately 18.5 K, is an order of magnitude greater than the maximum seen in the U- and Ce-based heavy-fermion systems may be natural. The large critical current displayed by PuCoGa5, which comes from radiation-induced self damage that creates pinning centres, would be of technological importance for applied superconductivity if the hazardous material plutonium were not a constituent.     

Quantum phase transition in a single-molecule quantum dot

Quantum criticality is the intriguing possibility offered by the laws of quantum mechanics when the wave function of a many-particle physical system is forced to evolve continuously between two distinct, competing ground states. This phenomenon, often related to a zero-temperature magnetic phase transition, is believed to govern many of the fascinating properties of strongly correlated systems such as heavy-fermion compounds or high-temperature superconductors. In contrast to bulk materials with very complex electronic structures, artificial nanoscale devices could offer a new and simpler means of understanding quantum phase transitions. Here we demonstrate this possibility in a single-molecule quantum dot, where a gate voltage induces a crossing of two different types of electron spin state (singlet and triplet) at zero magnetic field. The quantum dot is operated in the Kondo regime, where the electron spin on the quantum dot is partially screened by metallic electrodes. This strong electronic coupling between the quantum dot and the metallic contacts provides the strong electron correlations necessary to observe quantum critical behaviour. The quantum magnetic phase transition between two different Kondo regimes is achieved by tuning gate voltages and is fundamentally different from previously observed Kondo transitions in semiconductor and nanotube quantum dots. Our work may offer new directions in terms of control and tunability for molecular spintronics.     

伴金黄铁矿（Pyrite）结构的研究

应用多晶X射线衍射和Rietveld拟合和修正测定了含金与无金两类共20个黄铁矿样的精细结构。它们属于空间群T_h~6-Pa3。两类样品的晶胞参数无明显差别,平均值分别为a_0=5.4154(?)和a_0=5.4156(?),而硫原子坐标参数显著不等,含金的(?)_s=0.3849,无金的(?)_s=0.3868。依上述参数计算Fe-S和S-S键长,进而应用键价法算出结构中Fe离子的电价。结果说明含金的黄铁矿中Fe-S键短于五金的,而S-S键则相反;Fe离子价不相等,前者高于后者;大部分矿样中,Fe离子占有率小于1.000。在黄铁矿中容纳着上述离子变价和缺位等非完整性。因此就精细结构而言黄铁矿是一个具有不同程度非完整结构的系列。 含金矿样中Fe离子高于正二价的事实说明,当金以Au~(3+)(Au~+)迁移至含有Fe~(2+)和S_2~(2-)的热液体系中,Fe~(2+)部分地被氧化成Fe~(3+),而Au~(3+)(Au~+)被还原为Au与FeS_2共沉淀下来分散在黄铁矿晶格之外。     

惰性价电子效应的普遍性与规律性

本文系统研究了周期表中65种元素的有效核电荷,利用原子(或离子)的半径及电子的屏蔽效应和钻穿效应,讨论了惰性价电子效应产生的普遍性;并根据周期表中元素的性质,揭示了这一效应所表现出的规律性。     

Quantification of actinide alpha-radiation damage in minerals and ceramics

There are large amounts of heavy alpha-emitters in nuclear waste and nuclear materials inventories stored in various sites around the world. These include plutonium and minor actinides such as americium and curium. In preparation for geological disposal there is consensus that actinides that have been separated from spent nuclear fuel should be immobilized within mineral-based ceramics rather than glass because of their superior aqueous durability and lower risk of accidental criticality. However, in the long term, the alpha-decay taking place in these ceramics will severely disrupt their crystalline structure and reduce their durability. A fundamental property in predicting cumulative radiation damage is the number of atoms permanently displaced per alpha-decay. At present, this number is estimated to be 1,000-2,000 atoms/alpha in zircon. Here we report nuclear magnetic resonance, spin-counting experiments that measure close to 5,000 atoms/alpha in radiation-damaged natural zircons. New radiological nuclear magnetic resonance measurements on highly radioactive, 239Pu zircon show damage similar to that caused by 238U and 232Th in mineral zircons at the same dose, indicating no significant effect of half-life or loading levels (dose rate). On the basis of these measurements, the initially crystalline structure of a 10 weight per cent 239Pu zircon would be amorphous after only 1,400 years in a geological repository (desired immobilization timescales are of the order of 250,000 years). These measurements establish a basis for assessing the long-term structural durability of actinide-containing ceramics in terms of an atomistic understanding of the fundamental damage event.     

Ni_2MnIn合金电子结构和微观磁性的第一原理计算

利用基于密度泛函理论的第一原理赝势法,研究了Ni2MnIn合金Heusler结构和四方马氏体结构的晶体结构参数、电子结构及微观磁性特征.通过对能带、各原子轨道磁矩和分波态密度(PDOS)的计算分析,发现二种结构中各原子的原子轨道磁矩、元胞轨道磁矩、元胞体积均变化不明显,两相均具有明显自旋极化现象.计算表明:四方马氏体相变导致Ni2MnIn元胞费米能下降0.495eV;Ni2MnIn结构中,In原子具有弱抗磁性,晶胞磁矩为Mn原子轨道磁矩所主导,约占元胞总轨道磁矩85%,Ni原子轨道磁矩贡献约占元胞总轨道磁矩15%.理论计算结果与其他理论值进行了对比.     

原子系统基态能量和波函数的自洽场计算

本利用Hartree—Fock自洽场方法计算了原子序数Z＝2到Z＝9的原子以及对应各价离子的基态能量，计算结果与实验结果符合的较好，同时给出了处于基态的氧原子的各个价电子的波函数．     

Sub-kelvin optical cooling of a micromechanical resonator

Micromechanical resonators, when cooled down to near their ground state, can be used to explore quantum effects such as superposition and entanglement at a macroscopic scale. Previously, it has been proposed to use electronic feedback to cool a high frequency (10 MHz) resonator to near its ground state. In other work, a low frequency resonator was cooled from room temperature to 18 K by passive optical feedback. Additionally, active optical feedback of atomic force microscope cantilevers has been used to modify their response characteristics, and cooling to approximately 2 K has been measured. Here we demonstrate active optical feedback cooling to 135 +/- 15 mK of a micromechanical resonator integrated with a high-quality optical resonator. Additionally, we show that the scheme should be applicable at cryogenic base temperatures, allowing cooling to near the ground state that is required for quantum experiments--near 100 nK for a kHz oscillator.     

原子及轨道电亲性：新能量标度及其相关分析

应用原子的平均电离能来近似度量电亲性或电负性。所提出的电亲性新标度XLL与总电离能U除以原子价壳层电子数目N即平均电离能B成正比，进一步地从原子总电离能T或平均电离能B可确定其价与杂化轨道电亲性。它们虽支接从基态自由原子计算得到，却与从热化学数据得到的鲍林电负性颇为一致，因而计算上避免了其经验性，也可方便地计算惰性元素的电亲性，应用上同样具有广适性，并已显示出其优越性和独到处。     

确定原子光谱项的简易方法

本文给出了两种确定原子光谱项的简易方法,其一是从两个非同科电子的光谱项出发,选取两个同科电子光谱项的法则,并对其依据给予量子力学的证明;其二是从电子组态直接推求原子基态光谱项的公式。     

Bipolar supercurrent in graphene

Graphene--a recently discovered form of graphite only one atomic layer thick--constitutes a new model system in condensed matter physics, because it is the first material in which charge carriers behave as massless chiral relativistic particles. The anomalous quantization of the Hall conductance, which is now understood theoretically, is one of the experimental signatures of the peculiar transport properties of relativistic electrons in graphene. Other unusual phenomena, like the finite conductivity of order 4e(2)/h (where e is the electron charge and h is Planck's constant) at the charge neutrality (or Dirac) point, have come as a surprise and remain to be explained. Here we experimentally study the Josephson effect in mesoscopic junctions consisting of a graphene layer contacted by two closely spaced superconducting electrodes. The charge density in the graphene layer can be controlled by means of a gate electrode. We observe a supercurrent that, depending on the gate voltage, is carried by either electrons in the conduction band or by holes in the valence band. More importantly, we find that not only the normal state conductance of graphene is finite, but also a finite supercurrent can flow at zero charge density. Our observations shed light on the special role of time reversal symmetry in graphene, and demonstrate phase coherent electronic transport at the Dirac point.     

AB INITIO STUDY ON VALENCE INDICES AND REACTIVITIES OF SOME BORAENS

In the pressnt paper, 3-21G ab initio molecular orbital calculations are performed on diborane B_2H_6 and the substituted bridged-atom species H_4B_2X_2(X=F, Cl, OH, NH_2, CH_3), and these geometries are optimized with the energy gradient technique. According to the quantum chemical definition of atomic valence, the valences of the bridged-atoms are calculated to study the characteristion of the bridging bond B-X-B. Some larger boranes B_4H_(10), B_5H_9, and B_5H_(11) are also calculated to discuss the valence indices and analyze the reactivities of the bridged-atoms.     

Orbital Kondo effect in carbon nanotubes

Progress in the fabrication of nanometre-scale electronic devices is opening new opportunities to uncover deeper aspects of the Kondo effect--a characteristic phenomenon in the physics of strongly correlated electrons. Artificial single-impurity Kondo systems have been realized in various nanostructures, including semiconductor quantum dots, carbon nanotubes and individual molecules. The Kondo effect is usually regarded as a spin-related phenomenon, namely the coherent exchange of the spin between a localized state and a Fermi sea of delocalized electrons. In principle, however, the role of the spin could be replaced by other degrees of freedom, such as an orbital quantum number. Here we show that the unique electronic structure of carbon nanotubes enables the observation of a purely orbital Kondo effect. We use a magnetic field to tune spin-polarized states into orbital degeneracy and conclude that the orbital quantum number is conserved during tunnelling. When orbital and spin degeneracies are present simultaneously, we observe a strongly enhanced Kondo effect, with a multiple splitting of the Kondo resonance at finite field and predicted to obey a so-called SU4 symmetry.     

原子外层空轨道相对最稳定顺序及周期性规则

本文提出原子外层空轨道相对稳定性可作为电子填充的粗略判据;给出由中性原子轨道能数据直接导出原子外层轨道相对最稳定顺序的图表及周期性规则;用以简明、清晰、合理地推引解释元素基组态和解释元素周期律。提出在中心势场模型基础上推引全部元素基组态的方法。     

Direct observation of Tomonaga-Luttinger-liquid state in carbon nanotubes at low temperatures

The electronic transport properties of conventional three-dimensional metals are successfully described by Fermi-liquid theory. But when the dimensionality of such a system is reduced to one, the Fermi-liquid state becomes unstable to Coulomb interactions, and the conduction electrons should instead behave according to Tomonaga-Luttinger-liquid (TLL) theory. Such a state reveals itself through interaction-dependent anomalous exponents in the correlation functions, density of states and momentum distribution of the electrons. Metallic single-walled carbon nanotubes (SWNTs) are considered to be ideal one-dimensional systems for realizing TLL states. Indeed, the results of transport measurements on metal-SWNT and SWNT-SWNT junctions have been attributed to the effects of tunnelling into or between TLLs, although there remains some ambiguity in these interpretations. Direct observations of the electronic states in SWNTs are therefore needed to resolve these uncertainties. Here we report angle-integrated photoemission measurements of SWNTs. Our results reveal an oscillation in the pi-electron density of states owing to one-dimensional van Hove singularities, confirming the one-dimensional nature of the valence band. The spectral function and intensities at the Fermi level both exhibit power-law behaviour (with almost identical exponents) in good agreement with theoretical predictions for the TLL state in SWNTs.     

Li_2,Na_2和NaLi分子基态及低激发态的结构与势能函数

采用群论及原子分子反应静力学方法,推导了Li2、Na2和NaLi分子基态及低激发态的电子态及相应的离解极限,运用二次组态相互作用方法(QCISD)优化计算了Li2、Na2和NaLi分子基态的平衡结构、振动频率和离解能,并对Li2、Na2和NaLi分子基态进行了单点能扫描计算,激发态则用CIS方法,给出了各分子的Murrell-Sor-bie函数形式的完整势能函数,计算出与基态和低激发态相对应的光谱常数(Be,αe,ωe和ωeχe),结果与实验数据符合得相当好.     

NH2自由基电子基态及激发态解离通道的静力学分析

本文利用原子分子反应静力学的基本原理,研究了NH2自由基体系的可能解离通道,得到了NH2自由基电子基态2B1及第一激发态2A1合理的解离通道。