High-temperature superconductivity in lattice-expanded C60

C60 single crystals have been intercalated with CHCl3 and CHBr3 in order to expand the lattice. High densities of electrons and holes have been induced by gate doping in a field-effect transistor geometry. At low temperatures, the material turns superconducting with a maximum transition temperature of 117 K in hole-doped C60/CHBr3. The increasing spacing between the C60 molecules follows the general trend of alkali metal-doped C60 and suggests routes to even higher transition temperatures.     

The structure of the c60 molecule: x-ray crystal structure determination of a twin at 110 k

Single-crystal x-ray diffraction methods were used to determine the crystal and molecular structure of C(60) buckminsterfullerene. At 110 kelvin C(60) is cubic, apparent Laue symmetry m3m, but it exhibits noncrystallographic systematic extinctions indicative of a twin in which I(hkl) and I(khl) are superimposed. In fact, C(60) crystallizes with four molecules in space group [See equation in the PDF file] of the cubic system (Laue symmetry m3) with lattice constant a = 14.052(5) angstroms (A) at 110 kelvin. The twin components are equal. A given component, which has crystallographically imposed symmetry [See equation in the PDF file] displays an ordered structure of a truncated icosahedron. The five independent C=C bonds that join C(6) rings average 1.355(9) A; the ten independent C-C bonds that join C(6) and C(5) rings average 1.467(21) A. The mean atom-to-atom diameter of the C(60) molecule is 7.065(3) A. The molecules are very tightly packed in the crystal structure, with intermolecular C...C distances as short as 3.131(7) A.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

采用变温X射线衍射技术对六方钛酸钡陶瓷材料的结构监控

对于由冷压陶瓷技术所开发的纯六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，采用变温XRD技术测量该陶瓷在不同温度下的XRD谱，鉴定晶体结构．澄清了六方钛酸钡（BaTiO3）介电陶瓷材料的晶体结构是否在BaTiO3的居里温度（n=130℃）发生结构相变，并验证开发的变温X射线衍射（XRD）技术在无机粉体材料结构监控的可行性．结果表明：BaTiO3陶瓷在Tc发生四方-立方的结构相变，以45°附近两个分立的（002）／（200）衍射峰演变为单一对称的（200）衍射峰为标志；而六方Ba（Ti0.95Fe0.05）O3-δ陶瓷直到300℃都不发生结构相变．对于六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，升高温度并不能导致吸附环境氧来填充氧空位，Fe3＋Vo-Fe3＋缺陷复合体所维持的晶格电中性仍占据统治地位，六方-立方结构相变不发生．该项研究为变温XRD技术在工业生产上对无机粉体材料的监控应用提供了技术依据．     

Magnetic susceptibility of molecular carbon: nanotubes and fullerite

Elemental carbon can be synthesized in a variety of geometrical forms, from three-dimensional extended structures (diamond) to finite molecules (C(60) fullerite). Results are presented here on the magnetic susceptibility of the least well-understood members of this family, nanotubes and C(60) fullerite. (i) Nanotubes represent the cylindrical form of carbon, intermediate between graphite and fullerite. They are found to have significantly larger orientation-averaged susceptibility, on a per carbon basis, than any other form of elemental carbon. This susceptibility implies an average band structure among nanotubes similar to that of graphite. (ii) High-resolution magnetic susceptibility data on C(60) fullerite near the molecular orientational-ordering transition at 259 K show a sharp jump corresponding to 2.5 centimeter-gram-second parts per million per mole of C(60). This jump directly demonstrates the effect of an intermolecular cooperative transition on an intramolecular electronic property, where the susceptibility jump may be ascribed to a change in the shape of the molecule due to lattice forces.     

Motions of molecules in liquids: viscosity and diffusivity

The fluidity of a simple liquid is proportional to its degree of expansion over the volume, V(0), at which its molecules are so crowded as to inhibit self-diffusion and viscous (as distinguished from plastic) flow. The equation of proportionality is 1/eta = B[(V - V(0))/V(0)] where eta is the viscosity and V is the molal volume. Values of B are the same for normal paraffins from C(3)H(8) to C(7)H(16) and then decrease progressively as the paraffin lengths increase. Values for other liquids, C(6)H(6), CCl(4), P(4), CS(2), CHCl(3), and Hg, appear to vary with repulsive forces. liquids can be moderately fluid when expanded by less than 10 percent; this shows the unreality of some theoretical treatments of the liquid state. Diffusivity begins from the temperature at which V equals V(0) and can be correlated for temperature dependence, and for solute-solvent interrelations.     

桂花、白兰叶表皮污染物去除方法的比较

研究了不同试剂及不同处理时间对桂花和白兰叶表皮污染物的清除效果.扫描电镜观察结果表明,采用CHC l3处理对桂花叶表皮污染物清除效果最佳,其次是C8H10;C8H10对白兰叶表皮污染物清除效果比CHC l3好.4种清洗剂对桂花和白兰叶表皮污染物处理时间要求不同,桂花处理3或6 h都能达到清除污染物的目的,而白兰处理2 h即可.4种清洗剂处理后再经30 m in超声波清洗,效果更佳.     

Probing nanoscale ferroelectricity by ultraviolet Raman spectroscopy

We demonstrated that ultraviolet Raman spectroscopy is an effective technique to measure the transition temperature (Tc) in ferroelectric ultrathin films and superlattices. We showed that one-unit-cell-thick BaTiO3 layers in BaTiO3/SrTiO3 superlattices are not only ferroelectric (with Tc as high as 250 kelvin) but also polarize the quantum paraelectric SrTiO3 layers adjacent to them. Tc was tuned by approximately 500 kelvin by varying the thicknesses of the BaTiO3 and SrTiO3 layers, revealing the essential roles of electrical and mechanical boundary conditions for nanoscale ferroelectricity.     

Visualization of the molecular Jahn-Teller effect in an insulating K4C60 monolayer

We present a low-temperature scanning tunneling microscopy (STM) study of K(x)C60 monolayers on Au(111) for 3 < or = x < or = 4. The STM spectrum evolves from one that is characteristic of a metal at x = 3 to one that is characteristic of an insulator at x = 4. This electronic transition is accompanied by a dramatic structural rearrangement of the C60 molecules. The Jahn-Teller effect, a charge-induced mechanical deformation of molecular structure, is directly visualized in the K4C60 monolayer at the single-molecule level. These results, along with theoretical analyses, provide strong evidence that the transition from metal to insulator in K(x)C60 monolayers is caused by the Jahn-Teller effect.     

Au20: a tetrahedral cluster

Photoelectron spectroscopy revealed that a 20-atom gold cluster has an extremely large energy gap, which is even greater than that of C60, and an electron affinity comparable with that of C60. This observation suggests that the Au20 cluster should be highly stable and chemically inert. Using relativistic density functional calculations, we found that Au20 possesses a tetrahedral structure, which is a fragment of the face-centered cubic lattice of bulk gold with a small structural relaxation. Au20 is thus a unique molecule with atomic packing similar to that of bulk gold but with very different properties.     

Compressibility of M3C60 Fullerene Superconductors: Relation Between Tc and Lattice Parameter

X-ray diffraction and diamond anvil techniques were used to measure the isothermal compressibility of K(3)C(60) and Rb(3)C(60), the superconducting, binary alkali-metal intercalation compounds of solid buckminsterfullerene. These results, combined with the pressure dependence of the superconducting onset temperature T(c) measured by other groups, establish a universal first-order relation between T(c) and the lattice parameter a over a broad range, between 13.9 and 14.5 angstroms. A small secondorder intercalate-specific effect was observed that appears to rule out the participation of intercalate-fullerene optic modes in the pairing interaction.     

稻叶表皮蜡质提取方法及含量的比较

以水稻成熟叶片为材料,用氯仿和正己烷两种溶剂,采用常温法、加热法和常温加热结合法提取稻叶表皮蜡质.结果表明,氯仿作溶剂的提取效果好于正己烷,常温加热结合法提取表皮蜡质含量最高,加热法居中,常温法最低.扫描电镜观察结果表明,采用常温加热结合法,用两种溶剂都能将叶表皮蜡质完全提取干净;采用加热法,用氯仿为溶剂能将叶表皮蜡质提取干净,而用正己烷为溶剂,叶片表皮蜡质还有少量呈不规则的小粒状残存;用常温法则两种溶剂都不能将稻叶表皮蜡质提取干净.提取时间对蜡质提取效果有明显影响,高温下(氯仿60℃或正己烷67℃)提取超过30 s,导致细胞内脂溶性成分渗出.综合蜡质含量和扫描电镜分析的结果,以氯仿为溶剂、60℃30 s提取是有效且简单易行的稻叶表皮蜡质提取方法.     

Orientational Disorder of C60 in Li2CsC60

The x-ray diffraction of the nonsuperconducting ternary fulleride Li(2)CsC(60) reveals at room temperature a face-centered-cubic (Fm3m) disordered structure that persists to a temperature of 13 Kelvin. The crystal structure is best modeled as containing quasispherical [radius of 3.556(4) angstroms] C(60)(3-) ions, in sharp contrast to their orientational state in superconducting face-centered-cubic K(3)C(60) (merohedral disorder) and primitive cubic Na(2)CsC(60) (orientational order). The orientational disorder of the carbon atoms on the C(60)(3-) sphere was analyzed with symmetry-adapted spherical-harmonic functions. Excess atomic density is evident in the <111> directions, indicating strong bonding Li(+)-C interactions, not encountered before in any of the superconducting alkali fullerides. The intercalate-carbon interactions and the orientational state of the fullerenes have evidently affected the superconducting pair-binding mechanism in this material.     

Superconductivity at 45 k in rb/tl codoped c60 and c60/c70 mixtures

The appearance of superconductivity at relatively high temperatures in alkali metal-doped C(60) fullerene provides the challenge to both understand the nature and origin of the superconductivity and to determine the upper limit of the superconducting transition temperature (T(c)). Towards the latter goal, it is shown that doping with potassium-thallium and rubidium-thallium alloys in the 400 to 430 degrees C temperature range increases the T(c) of C(60)/C(70) mixtures to 25.6 K and above 45 K, respectively. Similar increases in T(c) were also observed upon analogous doping of pure C(60). Partial substitution of potassium with thallium in interstitial sites between C(60) molecules is suggested by larger observed unit cell parameters than for the K(3)C(60) and K(4)C(60) phases. Contrary to previous results for C(60) doped with different alkali metals, such expansion does not alone account for the changes in critical temperature.     

Spin-orbital short-range order on a honeycomb-based lattice

Frustrated magnetic materials, in which local conditions for energy minimization are incompatible because of the lattice structure, can remain disordered to the lowest temperatures. Such is the case for Ba(3)CuSb(2)O(9), which is magnetically anisotropic at the atomic scale but curiously isotropic on mesoscopic length and time scales. We find that the frustration of Wannier's Ising model on the triangular lattice is imprinted in a nanostructured honeycomb lattice of Cu(2+) ions that resists a coherent static Jahn-Teller distortion. The resulting two-dimensional random-bond spin-1/2 system on the honeycomb lattice has a broad spectrum of spin-dimer-like excitations and low-energy spin degrees of freedom that retain overall hexagonal symmetry.     

Atmospheric residence time of CH3Br estimated from the junge spatial variability relation

The atmospheric residence time for methyl bromide (CH3Br) has been estimated as 0.8 +/- 0.1 years from its empirical spatial variability relative to C2H6, C2Cl4, CHCl3, and CH3Cl. This evaluation of the atmospheric residence time, based on Junge's 1963 general proposal, provides an estimate for CH3Br that is independent of source and sink estimates. Methyl bromide from combined natural and anthropogenic sources furnishes about half of the bromine that enters the stratosphere, where it plays an important role in ozone destruction. This residence time is consistent with the 0.7-year value recently calculated for CH3Br from the combined strength estimates for its known significant sinks.     

High-temperature ferromagnetism in CaB2C2

We report a high Curie-temperature ferromagnet, CaB2C2. Although the compound has neither transition metal nor rare earth ions, the ferromagnetic transition temperature Tc is about 770 Kelvin. Despite this high T(c), the magnitude of the ordered moment at room temperatures is on the order of 10(-4) Bohr magneton per formula unit. These properties are rather similar to those of doped divalent hexaborides, such as Ca(1-x)La(x)B6. The calculated electronic states also show similarity near the Fermi level between CaB2C2 and divalent hexaborides. However, there is an important difference: CaB2C2 crystallizes in a tetragonal structure, and there are no equivalent pockets in the energy bands for electrons and holes-in contrast with CaB6. Thus, the disputed threefold degeneracy, specific to the cubic structure, in the energy bands of divalent hexaborides turns out not to be essential for high-temperature ferromagnetism. It is the peculiar molecular orbitals near the Fermi level that appear to be crucial to the high-Tc ferromagnetism.     

Colossal positive and negative thermal expansion in the framework material Ag3[Co(CN)6

We show that silver(I) hexacyanocobaltate(III), Ag3[Co(CN)6], exhibits positive and negative thermal expansion an order of magnitude greater than that seen in other crystalline materials. This framework material expands along one set of directions at a rate comparable to the most weakly bound solids known. By flexing like lattice fencing, the framework couples this to a contraction along a perpendicular direction. This gives negative thermal expansion that is 14 times larger than in ZrW2O8. Density functional theory calculations quantify both the low energy associated with this flexibility and the role of argentophilic (Ag+...Ag+) interactions. This study illustrates how the mechanical properties of a van der Waals solid might be engineered into a rigid, useable framework.     

Packing C60 in boron nitride nanotubes

We have created insulated C60 nanowire by packing C60 molecules into the interior of insulating boron nitride nanotubes (BNNTs). For small-diameter BNNTs, the wire consists of a linear chain of C60 molecules.With increasing BNNT inner diameter, unusual C60 stacking configurations are obtained (including helical, hollow core, and incommensurate) that are unknown for bulk or thin-film forms of C60.C60 in BNNTs thus presents a model system for studying the properties of dimensionally constrained "silo" crystal structures. For the linear-chain case, we have fused the C60 molecules to form a single-walled carbon nanotube inside the insulating BNNT.     

Probing c60

Experiments involving the laser vaporization of graphite have indicated that one particular duster of carbon, C(60), is preeminently stable; this special stability may be evidence that C(60) can readily take the form of a hollow truncated icosahedron (a sort of molecular soccerball). If true, this structure for C(60) would be the first example of a spherical aromatic molecule. In fact, because of symmetry properties unique to the number 60, it may be the most perfecty spherical, edgeless molecule possible. Its rapid formation in condensing carbon vapors and its extreme chemical and photophysical stability may have far-reaching implications in a number of areas, particularly combustion science and astrophysics. For these reasons C(60) and other dusters of carbon have continued to be the subject of intense research. This article provides a short review of the many new experimental probes of the properties of C(60) and related carbon dusters.