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1.
On the basis of semiempirical and high-level ab initio calculations, theoretical evidence is presented of a "window" mechanism operable on the surface of C(60) and other fullerenes. Through this mechanism, large holes may be formed in fullerenes excited to their triplet state, openings through which atoms and small molecules can pass. This work provides a theoretical foundation for experiments that have prepared endohedral noble gas compounds of C(60) under thermal excitation. A method is proposed that could increase the efficiency of the process of noble gas insertion into C(60) and provide a more general means to create endohedral fullerene compounds. 相似文献
2.
Photoemission spectra of compounds prepared by the reaction of C(60) films with calcium show two distinct metallic phases, whereas alkali-doped C(60) films have only one. In the first phase the bulk t(1u) band, derived from the lowest unoccupied molecular orbital of C(60), is partially occupied. This is followed by an insulating phase that has the composition Ca(3)C(60) in which the t(1u) band is filled and has properties analogous to those of K(6)C(60). Continued exposure to calcium produces a second metallic phase in which electrons are donated into the t(1g) band. The superconductivity of Ca(5)C(60) is associated with the t(1g) band. 相似文献
3.
We analyzed the transport of ballistic electrons through organic molecules on uniformly flat surfaces of bismuth grown on silicon. For the fullerene C60 and for a planar organic molecule (3,4,9,10-perylene-tetracarboxylic acid dianhydride), the signals revealed characteristic submolecular patterns that indicated where ballistic transport was enhanced or attenuated. The transport was associated to specific electronic molecular states. At electron energies of a few electron volts, this "scanning near-field electron transmission microscopy" method could be applied to various adsorbates or thin layers. 相似文献
4.
Anderson PW 《Science (New York, N.Y.)》1987,235(4793):1196-1198
The oxide superconductors, particularly those recently discovered that are based on La(2)CuO(4), have a set of peculiarities that suggest a common, unique mechanism: they tend in every case to occur near a metal-insulator transition into an odd-electron insulator with peculiar magnetic properties. This insulating phase is proposed to be the long-sought "resonating-valence-bond" state or "quantum spin liquid" hypothesized in 1973. This insulating magnetic phase is favored by low spin, low dimensionality, and magnetic frustration. The preexisting magnetic singlet pairs of the insulating state become charged superconducting pairs when the insulator is doped sufficiently strongly. The mechanism for superconductivity is hence predominantly electronic and magnetic, although weak phonon interactions may favor the state. Many unusual properties are predicted, especially of the insulating state. 相似文献
5.
Tycko R Dabbagh G Rosseinsky MJ Murphy DW Fleming RM Ramirez AP Tully JC 《Science (New York, N.Y.)》1991,253(5022):884-886
The results of (13)C nuclear magnetic resonance (NMR) measurements on alkali fullerides KxC(60) are reported. The NMR spectra demonstrate that material with 0 < x < 3 is in fact a two-phase system at equilibrium, with x = 0 and x = 3. NMR lineshapes indicate that C(3-)(60) ions rotate rapidly in the K(3)C(60) phase at 300 K, while C(6)-(60) ions in the insulating K(6)C(60) phase are static on the time scale of the lineshape measurement. The temperature dependence of the (13)C spin-lattice relaxation rate in the normal state of K(3)C(60) is found to be characteristic of a metal, indicating the important role of the C(3-)(60) ions in the conductivity. From the relaxation measurements, an estimate of the density of electronic states at the Fermi level is derived. 相似文献
6.
The atomic electron orbitals that underlie molecular bonding originate from the central Coulomb potential of the atomic core. We used scanning tunneling microscopy and density functional theory to explore the relation between the nearly spherical shape and unoccupied electronic structure of buckminsterfullerene (C60) molecules adsorbed on copper surfaces. Besides the known pi* antibonding molecular orbitals of the carbon-atom framework, above 3.5 electron volts we found atomlike orbitals bound to the core of the hollow C60 cage. These "superatom" states hybridize like the s and p orbitals of hydrogen and alkali atoms into diatomic molecule-like dimers and free-electron bands of one-dimensional wires and two-dimensional quantum wells in C60 aggregates. We attribute the superatom states to the central potential binding an electron to its screening charge, a property expected for hollow-shell molecules derived from layered materials. 相似文献
7.
Iwasa Y Arima T Fleming RM Siegrist T Zhou O Haddon RC Rothberg LJ Lyons KB Carter HL Hebard AF Tycko R Dabbagh G Krajewski JJ Thomas GA Yagi T 《Science (New York, N.Y.)》1994,264(5165):1570-1572
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. 相似文献
8.
We report here on a novel realization of a field-effect device that allows switching between insulating and superconducting states, which is the widest possible variation of electrical properties of a material. We chose C(60) as the active material because of its low surface state density and observed superconductivity in alkali metal-doped C(60). We induced three electrons per C(60) molecule in the topmost molecular layer of a crystal with the field-effect device, creating a superconducting switch operating up to 11 kelvin. An insulator was thereby transformed into a superconductor. This technique offers new opportunities for the study of superconductivity as a function of carrier concentration. 相似文献
9.
绝缘接头或绝缘法兰是管道阴极保护中必不可少的重要管件，但在现场安装时都曾出现过绝缘性达不到替代洒求值的问题。对此现象进行了剖析，指出影响电绝缘性的主要原因是绝缘连接头的绝缘材料制造，装配等方面的质量问题。 相似文献
10.
Dinnebier RE Gunnarsson O Brumm H Koch E Stephens PW Huq A Jansen M 《Science (New York, N.Y.)》2002,296(5565):109-113
CHCl3 and CHBr3 intercalated C60 have attracted particular interest after a superconductivity transition temperature (Tc) of up to 117 K was discovered. We have determined the structure using synchrotron x-ray powder-diffraction and found that the expansion of the lattice mainly takes place in one dimension (triclinic b axis), leaving planes of C60 molecules on an approximately hexagonal, slightly expanded lattice. We have performed tight-binding band structure calculations for the surface layer. In spite of the slight expansion of the layers, for the range of dopings where a large Tc has been observed, the density of states at the Fermi energy is smaller for C60.2CHCl3 and C60.2CHBr3 than for C60. This suggests that the lattice expansion alone cannot explain the increase of Tc. 相似文献
11.
Weltner W 《Science (New York, N.Y.)》1967,155(3759):155-164
Optical spectroscopy of stellar molecules trapped at 4 degrees K is particularly valuable when the data can be used to complement the corresponding gas data. The ground state is then directly established by measurement of the absorption spectrum at the low temperature, since all transitions beginning from excited states are eliminated. Isotopic substitution establishes the (0,0) bands of transitions to excited electronic states, and when these data are combined with infrared and fluorescence measurements at 4 degrees K, most of the vibrational properties of the ground and excited states can be obtained. Of the many examples cited and discussed here, C(3) is perhaps the most outstanding. Because the various molecules trapped in matrices are usually identified through prior mass spectrometric work, the optical observations often lead to the discovery of band systems of molecules whose spectra have not previously been observed-for example, those of Si(2)C(3), TaO(2), and WO(2). In these cases the location of the spectral regions in which molecular transitions appear may also serve to encourage the gas spectroscopist to further exploration with high-dispersion spectrographs. I share Ramsay's view (4, p. 204) that further investigation of f-number determinations from matrix spectra should be encouraged, particularly because of the lack of such data for molecules in stars. The principal source of error probably lies in the estimation of the number of molecules per square centimeter in the matrix, but no real test of this has been made. The only existing f values from matrix spectra are those for the C(3) (43, 44) and C(2) (51) molecules, and these are not ideal for test purposes. Because of the anomalous nature of the matrix results discussed above, the rather good agreement between f values for the solid and gas phases of C(2) (51) cannot be considered as support for the matrix determinations. What is needed is a matrix determination of several f(v'v") values (that is, determinations for specific bands) for molecules such as CN and NO or, preferably, for a gas vaporized at high temperature, for which these f values are relatively well established in the gas phase. In this connection the possibility of determining other molecular properties in matrices comes to mind. However, it has been clearly shown that the shape of the potential energy function in the electronic states of molecules can be affected when molecules are trapped in matrices. Brewer, Brabson, and Meyer, in work on S(2) (55), and Schnepp and Dressler, in work on O(2) (56), have examined the anharmonicity in matrices over many vibrational levels. Distortion of the gas potential energy curves occurs in the heavier matrices and sometimes at high vibrational levels in the light ones. Recently work has been begun on comparing the Franck-Condon factors connecting the ground state and two excited states of ScF trapped in a neon matrix (57) with factors calculated from the gas-spectrum data of R. F. Barrow et al. (58) (Deltar(e), the change in interatomic distance upon excitation, has a relatively large value of ~ 0.1 A in these systems). As is well known, such factors are particularly sensitive to the value of Deltar(e), but differences in anharmonicity do not, however, have as significant an effect upon the Franck-Condon factors. Hence a comparison of the matrix and gas factors will lead to further information about matrix effects and will indicate whether Franck-Condon factors can be obtained from matrix spectra. One of the important problems in the study of stellar molecules is the determination of the low-lying electronically excited states, similar to the (1)Delta <--> X(3)Delta difference (~ 580 cm(-1)) in TiO measured by Phillips. Most of the transition-metal oxides have such low-lying levels, and they must be taken into consideration in any calculation of thermodynamic effects at high temperature. It appears that the study of emission spectra in the infrared at 4 degrees K may be one approach to this problem, and an attempt is now being made to confirm the TiO value in order to test the method. Perhaps the greatest advantage of matrix-isolation is the fact that it allows study of these molecules-or of any molecules difficult to produce in a microwave cavity-by electron-paramagnetic-resonance spectroscopy. Study of molecules by this means can provide information about ground state wave functions that is not obtainable by optical spectroscopy, as illustrated by the investigation of ScO, YO, and LaO. Also, it seems likely that the preferential orientation of molecules in matrices, which is probably achievable in most cases, will be a valuable asset in the study of the magnetic properties of molecules by electron-paramagneticresonance spectroscopy, regardless of whether the molecules are "hot" or "cold" (60). 相似文献
12.
Mihailovic D Arcon D Venturini P Blinc R Omerzu A Cevc P 《Science (New York, N.Y.)》1995,268(5209):400-402
Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C(60) molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis(dimethylamino)ethylene-C(60) (TDAE-C(60)) (Curie temperature T(c) = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C(60) molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of pi-lectron exchange interactions between spins on neighboring C(60) molecules, suggesting a microscopic origin for the observed spinglass behavior of the magnetic state. 相似文献
13.
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. 相似文献
14.
High-resolution Raman spectroscopy of polycrystalline films of C(60) deposited under ultrahigh-vacuum conditions show that the spectrum below 244 +/- 3 kelvin consists of a superposition of two components whose relative contributions are temperature-dependent. The spectrum of the more intense of the two components is similar to that obtained for air- or oxygen-exposed samples of C(60) at room temperature, whereas the spectrum above 244 +/- 3 kelvin corresponds to one previously reported for oxygen-free samples of C(60). The results may indicate an order-disorder phase transition involving the percolation of a cluster of C(60) molecules engaged in coherent Raman scattering. 相似文献
15.
Soldatov AV Roth G Dzyabchenko A Johnels D Lebedkin S Meingast C Sundqvist B Haluska M Kuzmany H 《Science (New York, N.Y.)》2001,293(5530):680-683
Polymeric forms of C60 are now well known, but numerous attempts to obtain C70 in a polymeric state have yielded only dimers. Polymeric C70 has now been synthesized by treatment of hexagonally packed C70 single crystals under moderate hydrostatic pressure (2 gigapascals) at elevated temperature (300 degrees C), which confirms predictions from our modeling of polymeric structures of C70. Single-crystal x-ray diffraction shows that the molecules are bridged into polymeric zigzag chains that extend along the c axis of the parent structure. Solid-state nuclear magnetic resonance and Raman data provide evidence for covalent chemical bonding between the C70 cages. 相似文献
16.
The synthesis of a new family of spheroidal carbon molecules derived from the fullerenes is described. The fulleroids are produced by incremental addition of a divalent carbon equivalent that has two phenyl (Ph) rings to fullerene C(60). The fulleroids Ph(2)C(61), Ph(4)C(62), Ph(6)C(63), Ph(8)C(64), Ph(10)C(65), and Ph(12)C(66) have been prepared and characterized. 相似文献
17.
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. 相似文献
18.
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. 相似文献
19.
Ramirez AP Haddon RC Zhou O Fleming RM Zhang J McClure SM Smalley RE 《Science (New York, N.Y.)》1994,265(5168):84-86
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. 相似文献
20.
Benning PJ Martins JL Weaver JH Chibante LP Smalley RE 《Science (New York, N.Y.)》1991,252(5011):1417-1419
The recent report of electrical conductivity in the alkali metal fullerides and the discovery of superconductivity at 18 K for KxC(60) has raised fundamental questions about the electronic states on either side of the Fermi level, their occupancy with K intercalation, and the mechanism of superconductivity. Direct photoemission evidence is presented of filling of bands derived from the lowest unoccupied molecular orbital as a function of K incorporation for the metallic and insulating phases. This filling is not rigid band-like, and it reflects disorder in the K sites. Theoretical analysis indicates that KxC(60) is a strong coupling superconductor, and we suggest that the enhanced electron-phonon interaction is related to the unique hybridization of the C sp-derived states. 相似文献