Raman Studies of Alkali-Metal Doped AxC60 Films (A = Na, K, Rb, and Cs; x = 0, 3, and 6)

The room temperature Raman spectra of the intramolecular modes between 100 cm(-1) and 2000 cm(-1) are reported for alkali-metal doped AxC(60) films. For A = K, Rb, and Cs, phase separation is observed with the spectra of C(60), K(3)C(60), K(6)C(60), Rb(3)C(60), Rb(6)C(60), and Cs(6)C(60) phases reported. The x = 3 phases show only three Raman active modes: two of Ag symmetry and only the lowest frequency Hg mode. The other Hg modes regain intensity in the x = 6 films, with several mode splittings observed. For A = Na, such phase separation is not clearly observed, and reduced mode shifts are interpreted as due to incomplete charge transfer in these films.     

Crystal Structure, Bonding, and Phase Transition of the Superconducting Na2CsC60 Fulleride

The crystal structure of superconducting Na(2)CsC(60) was studied by high-resolution powder neutron diffraction between 1.6 and 425 K. Contrary to the literature, the structure at low temperatures is primitive cubic [See equation in the PDF file], isostructural with pristine C(60). Anticlockwise rotation of the C(60) units by 98 degrees about [111] allows simultaneous optimization of C(60)-C(60) and alkali-fulleride interactions. Optimal Na(+)-C(60)(3-) coordination is achieved with each sodium ion located above one hexagon face and three hexagon-hexagon fusions of neighboring fulleride ions (coordination number 12). Reduction of the C(60) molecule lengthens the hexagon-hexagon fusions and shortens the pentagon-hexagon fusions (to approximately 1.43 angstroms). On heating, Na(2)CsC(60) undergoes a phase transition to a face-centered-cubic [See equation in the PDF file] phase, best modeled as containing quasi-spherical C(60)(3-) ions. The modified structure and intermolecular potential provide an additional dimension to the behavior of superconducting fullerides and should sensitively affect their electronic and conducting properties.     

X-ray diffaction evidence for nonstoichiometric rubidium-c60 intercalation compounds

Powder x-ray diffraction at 300 K on equilibrated samples of several nominal compositions chi in Rb(chi)C(60) is reported. In addition to the face-centered cubic (fcc) (chi = 3, superconducting), body-centered tetragonal (chi = 4), and body-centered cubic (bcc) (chi = 6) stoichiometric phases, direct evidence for a dilute fcc doped phase, 0 x c 相似文献   

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.     

C60 rotation in the solid state: dynamics of a faceted spherical top

The rotational dynamics of C(60) in the solid state have been investigated with carbon-13 nuclear magnetic resonance ((13)C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1(CSA)(1)) was precisely measured from the magnetic field dependence of T(1), allowing the molecular reorientational correlation time, tau, to be determined. At 283 kelvin, tau = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 10(10) per second. This reorientation time is only three times as long as the calculated tau for free rotation and is shorter than the value measured for C(60) in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C(60). In both phases tau showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.     

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.     

(RbxK1-x)3C60 Superconductors: Formation of a Continuous Series of Solid Solutions

By means of an approach that employs alkali-metal alloys, bulk single-phase (RbxK1-x)(3)C(6O) superconductors have been prepared for all x between 0 and 1. For x = 1 it is shown that the maximum superconducting fraction, which approaches 100% in sintered pellets, occurs at a Rb to C(60) ratio of 3:1. More importantly, single-phase superconductors are formed at all intermediate values of x, and it is shown that the transition temperature (T(c)) increases linearly with x in this series of materials. The formation of a continuous range of solid solutions demonstrates that the rubidium- and potassium-doped C(60) superconducting phases must be isostructural, and furthermore, suggests that the linear increase in T(c) with x results from a chemical pressure effect.     

Electrical Resistivity and Stoichiometry of CaxC60 and SrxC60 Films

The temperature- and concentration-dependent resistivities of annealed CaxC(60) and SrxC(60) films were measured near room temperature. Resistivity minima were observed at x = 2 and 5. The resistivities of these films were rho(min) approximately 1 ohm-centimeter for x = 2 and rho(min) approximately 10(-2) ohm-centimeter for x = 5. This latter value is comparable to the resistivities found in similar experiments on K(3)C(60) films. There is a maximum in the resistivity between x = 2 and 3, and another at x approximately 7. The conductivity is activated over the whole range of compositions, and the activation energy scales with the logarithm of the resistivity. The results suggest that the conductivity and superconductivity observed in Ca(5)C(60) are associated with the population of bands derived from the t(1g) level of C(6O).     

Electrical resistivity and stoichiometry of kkhgr c60 films

Electrical resistances of polycrystalline fullerene (C(60)) films were monitored while the films were being doped in ultrahigh vacuum with potassium from a molecular-beam effusion source. Temperature- and concentration-dependent resistivities of K(chi) C(60) films in equilibrium near room temperature were measured. The resistance changes smoothly from metallic at chi approximately 3 to activated as chi --> = 0 or chi --> 6. The minimum resistivity for K(3)C(60) films is 2.2 microohm-centimeters, near the Mott limit. The resistivities are interpreted in terms of a granular microstructure where K(3)C(60) regions form nonpercolating grains, except perhaps at chi approximately 3. Stoichiometries at the resistivity extrema were determined by ex situ Rutherford backscattering spectrometry to be chi = 3 +/- 0.05 at the resistance minimum and chi = 6 +/- 0.05 at the fully doped resistance maximum.     

A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

Submicrometer Superconducting YBa2Cu3O6+x Particles Made by a Low-Temperature Synthetic Route

Evidence suggests that superconducting, orthorhombic YBa(2)Cu(3)O(6+x)+ (x greater, similar 0.5) is always produced by oxidation of the oxygen-deficient, tetragonal form (x less, similar 0.5) of this phase (commonly referred to as 123). A synthetic route whereby solution-derived, carbon-free precursors are decomposed at 650 degrees to 700 degrees C in inert atmosphere to yield tetragonal 123 is now available. Appropriate precursors include hydrated oxides derived from the hydrolysis of organometallic solutions and aqueous solution-derived hyponitrites. Subsequent oxidation of the tetragonal phase at 400 degrees C results in submicrometer particles of orthorhombic 123. Superconductivity (T(c) onset approximately 87 K) has been confirmed in these materials by both Meissner effect and specific-heat measurements.     

Tunneling Spectroscopy of M3C60 Superconductors: The Energy Gap, Strong Coupling, and Superconductivity

Tunneling spectroscopy has been used to characterize the magnitude and temperature dependence of the superconducting energy gap (triangle up) for K(3)C(60) and Rb(3)C(60). At low temperature the reduced energy gap, 2triangle upkappaT(c) (where T(c) is the transition temperature) has a value of 5.3 +/- 0.2 and 5.2 +/- 0.3 for K(3)C(60) and Rb(3)C(60), respectively. The magnitude of the reduced gap for these materials is significantly larger than the value of 3.53 predicted by Bardeen-Cooper-Schrieffer theory. Hence, these results show that the pair-coupling interaction is strong in the M(3)C(60) superconductors. In addition, measurements of triangle up(T) for both K(3)C(60) and Rb(3)C(60) exhibit a similar mean-field temperature dependence. The characterization of triangle up and triangle up(T) for K(3)C(60) and Rb(3)C(60) provides essential constraints for theories evolving to describe superconductivity in the M(3)C(60) materials.     

Open Framework Structures Based on Sex2- Fragments: Synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, TI) in Molten (Ph4P)2Sex

Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C.     

关于不定方程5x(x+1)(x+2)(x+3)=18y(y+1)(y+2)(y+3)

运用Pell方程、递推序列、同余式及平方剩余等初等数论知识,证明了不定方程5x(x+1)(x+2)(x+3)=18y(y+1)(y+2)(y+3)仅有4组非平凡整数解(x,y)=(6, 4),(-9, 4),(6,-7),(-9,-7),同时给出该不定方程的全部整数解,分别为(x,y)=(0, 0),(0,-1),(0,-2),(0,-3),(-1, 0),(-1,-1),(-1,-2),(-1,-3),(-2, 0),(-2,-1),(-2,-2),(-2,-3),(-3, 0),(-3,-1),(-3,-2),(-3,-3),(6, 4),(-9, 4),(6,-7),(-9,-7).     

反相高效液相色谱法测定草莓天竺葵素 3 O 葡萄糖苷的含量

为了测定草莓中天竺葵素 3 O 葡萄糖苷的含量,建立了一种反相高效液相色谱法。采用Waters Symmetry C18色谱柱(5 μm, 46 mm × 150 mm),流动相A为10%甲酸,流动相B为乙腈。线性梯度洗脱设计为: 0～13 min,乙腈为0～20%,20 min,乙腈为40%,25 min,乙腈为0。检测波长为520 nm,进样量为每针20 μL,柱温25℃,流速为1 mL·min-1。结果表明,天竺葵素 3 O 葡萄糖苷在浓度为025～20 μg·mL-1范围内有良好的线性关系,线性回归方程为y=71　859x+13　792,相关系数为09993,回收率为9829%～ 10269%,相对偏差303。本测定方法简便、准确、快速、稳定,适合于测定草莓及其他蔬菜水果中天竺葵素 3 O葡萄糖苷的含量。     

Venus: absence of a phase effect at a 2-centimeter wavelength

Observations of Venus made during 1967 and 1968 at a frequency of 15.4 gigahertz set an upper limits of 5 percent for the variation of brightness temperature with phase. This negative result appears to contradict earlier detections of a phase effect. By comparison with Virg A (3C 274), which has an assumed flux density of 29 x 10(-26) watt per square meter per hertz, the brightness temperature of Venus at this frequency is 485 + 60, -40 degrees K (mean error).     

鲁北洼羊羔羊的屠宰率相关性研究

在毛皮生产最佳时期对鲁北洼羊羔羊进行了屠宰率、体尺及体重等测定，分析结果表明：①屠宰率与日龄相关显著（Ｐ＜０．０５），其回归方程为ｙ＝５０．１１－０．０５ｘ；②屠宰率与体高（ｘ１）、体长（ｘ２）、胸围（ｘ３）、十字部高（ｘ４）呈负相关；③屠宰率的估测公式为ｙ＝５４．５９０７－０．０１８０ｘ１－０．００８３ｘ２－０．００６７ｘ３－０．０１８０ｘ４（Ｐ＜０．０５）。     

Nuclear Resonance Properties of YBa2Cu3O6+x Superconductors

Nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) results for copper-63, oxygen-17, and yttrium-89 nuclei in the superconducting composition range of YBa(2)Cu(3)O(6+x) (0.4 相似文献   

保健系黑白花奶牛体重体尺生长模式及其与产乳性能相关性的研究

研究了保健系黑白花奶牛体重、体尺(体高、体斜长、胸围和管围)的生长模式及其间的相关性;并考虑了体重、体尺分别与305天产乳量的相关程度。结果表明:初生至三胎奶牛体重、体尺之间相关显著,五胎不显著。各阶段的体重、体尺与305天产乳量的相关性三胎显著,一、五胎不显著。     

Carbynes in meteorites: detection, low-temperature origin, and implications for interstellar molecules

Carbon from the Allende meteorite is not graphite but carbyne (triply bonded elemental carbon), inasmuch as on heating to 250 degrees to 330 degrees C it releases mainly triply bonded fragments: -(C identical withC)(n),- with n = 1 to 5, and -(C identical withC)(n)-CN, with n = 1 to 3. Although carbynes have been known to form only by condensation of carbon vapor above 2600 K or by explosive shock of > 600 kilobars, it is found that they also form metastably by the reaction 2CO --> CO(2) + C (solid) at 300 degrees to 400 degrees C in the presence of a chromite catalyst. Such low-temperature formation by surface catalysis may be the dominant source of carbynes on the earth and in meteorites, and a major source of interstellar carbynes and cyanopolyacetylenes.