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.     

Anionic constitution of 1-atmosphere silicate melts: implications for the structure of igneous melts

A structural model is proposed for the polymeric units in silicate melts quenched at 1 atmosphere. The anionic units that have been identified by the use of Raman spectroscopy are SiO(4)(4-) monomers, Si(2)O(7)(6-) dimers, SiO(3)(2-) chains or rings, Si(2)O(5)(2-) sheets, and SiO(2) three-dimensional units. The coexisting anionic species are related to specific ranges of the ratio of nonbridging oxygens to tetrahedrally coordinated cations (NBO/Si). In melts with 2.0 < NBO/Si < approximately 4.0, the equilibrium is of the type [See equation in the PDF file]. In melts with NBO/Si approximately 1.0 to 2.0, the equilibrium anionic species are given by [See equation in the PDF file]. In alkali-silicate melts with NBO/Si <~ 1.3 and in aluminosilicate melts with NBO/T < 1.0, where T is (Si + Al), the anionic species in equilibrium are given by [See equation in the PDF file]. In multicomponent melts with compositions corresponding to those of the major igneous rocks, the anionic species are TO(2), T(2)O(5), T(2)O(6), and TO(4), and the coexisting polymeric units are determined by the second and third of these disproportionation reactions.     

Corrections and clarifications

In the report "A three-dimensional model for the hammerhead ribozyme based on fluorescence measurements" by T. Tuschl et al. (4 Nov. 1994, p. 785), the text of lines 28 through 30 in column 3 on page 785 should have read, "... we located 5-carboxyfluorescein at (d, -29.5 degrees , L-3.75 A) and 5-carboxytetramethylrhodamine at (a, -29.5 degrees -delta, -3.75 A)." In the same report, the second line of equation 1 in the legend to figure 3 was incorrectly printed. The correct equation appears below. [See the equation in the PDF file] Equation 1 in note 17 of the same report was also incorrectly printed. The correct equation appears below. [see the equation in the PDF file].     

Synthesis and Single-Crystal X-ray Structure of a Highly Symmetrical C60 Derivative, C60Br24

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).     

Crystal and molecular structures of rhenium heptafluoride

Rhenium heptafluoride, ReF(7), is one of only two stable binary compounds MX(7) with a heptacoordinated metal atom M and halide atom X. Its low-temperature crystal structure, as determined by high-resolution powder neutron diffraction, reveals the molecular structure, which has been the subject of speculation and debate for many years. Here it is shown within experimental error that at 1.5 kelvin the lowest energy configuration of ReF(7) has symmetry Cs (m) and is a distorted pentagonal bipyramid. The deviation of the two axial Re-F bonds from collinear and the puckering of the ring of equatorial fluorine atoms are similar to what has been postulated as one of the conformations of the pseudorotational motion observed at higher temperatures.     

Erratum

In Kirk M. Wolter's Policy Forum ;;Accounting for America's uncounted and miscounted' (5 July, p. 12), there were two errors. The ;;Net undercount (%)' expression in the left column of page 13 should have read [See equation in the PDF file].     

Lithium, compression and high-pressure structure

Lithium is found to transform from a body-centered cubic (bcc) to a face-centered cubic (fcc) structure at 6.9 gigapascals (69 kilobars) and 296 kelvin. The relative volume of the bcc structured lithium at 6.9 gigapascals is 0.718, and the fcc structure is 0.25 percent denser. The bulk modulus and its pressure derivative for the bcc structure are 11.57 gigapascals and 3.4, and for the fcc structure are 13.1 gigapascals and 2.8. Extrapolation of the bcc-fcc phase boundary and the melting curve indicate a triple point around 15 gigapascals and 500 kelvin.     

Crystal structure of osmylated c60: confirmation of the soccer ball framework

An x-ray crystal structure that confirms the soccer ball-shaped carbon framework of C(60) (buckminsterfullerene) is reported. An osmyl unit was added to C(60) in order to break its pseudospherical symmetry and give an ordered crystal. The crystal structure of this derivative, C(60)(OsO(4))(4-tert-butylpyridine)(2), reveals atomic positions within the carbon cluster.     

Twinning in MgSiO3 Perovskite

Crystals of MgSiO(3) perovskite synthesized at high pressures and temperatures have orthorhombic symmetry under ambient conditions. Examination by transmission electron microscopy shows that the microstructure of crystals synthesized at 26 gigapascals and 1600 degrees C is dominated by a large number of twin domains that are related by reflection operations with respect to {112} and {110} planes. These twins may be associated with the transformations of MgSiO(3) perovskite from the cubic to tetragonal and tetragonal to orthorhombic phases, respectively, upon decreasing pressure and temperature. These observations suggest that under the experimental synthesis conditions, and perhaps in the earth's lower mantle, the stable phase of MgSiO(3) might have the cubic perovskite structure.     

MgB2 superconducting thin films with a transition temperature of 39 kelvin

We fabricated high-quality c axis-oriented epitaxial MgB2 thin films using a pulsed laser deposition technique. The thin films grown on (1 i 0 2) Al2O3 substrates have a transition temperature of 39 kelvin. The critical current density in zero field is approximately 6 x 10(6) amperes per cubic centimeter at 5 kelvin and approximately 3 x 10(5) amperes per cubic centimeter at 35 kelvin, which suggests that this compound has potential for electronic device applications, such as microwave devices and superconducting quantum interference devices. For the films deposited on Al2O3, x-ray diffraction patterns indicate a highly c axis-oriented crystal structure perpendicular to the substrate surface.     

Corrections and clarifications

Figure 2 on page 523 of the Report "Magnetoferritin: In vitro synthesis of a novel magnetic protein" by F. C. Meldrum et al. (24 July, p. 522) was incorrect. The correct figure is printed below. [See figure in the PDF file].     

Corrections and clarifications

The figure accompanying the 28 May Perspective "Apoptosis in AIDS" by M.-L. Gougeon and L. Montagnier (p. 1269) contained some errors. A corrected figure appears below. [See figure in the PDF file].     

Xenon Hexafluoride: Structure of a Cubic Phase at -80{degrees}C

The crystal structure of a cubic phase of composition XeF(6) has been determined at -80 degrees C. There are no simple molecules in the complex structure which involves 1008 atoms distributed over 1600 positions per unit cell. Ions of XeF(5)+ and F- are associated in tetrameric and hexameric rings of point group symmetries 4 and 32, respectively. The structure contains right-and left-handed conformations of both tetramers and hexamers. The handedness of the tetramers is dis-ordered but the orientation is ordered. The handedness of the hexamers is ordered but the orientation is disordered.     

Order-disorder transition in polycrystalline c60 films

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.     

Order and Disorder in C60 and KxC60 Multilayers: Direct Imaging with Scanning Tunneling Microscopy

Monolayer and multilayer structures of C(60), a high temperature van der Waals solid, have been studied with scanning tunneling microscopy. Structures grown on GaAs(110) at 300 kelvin and at elevated temperatures show significantly different morphologies because of balances between thermodynamics and kinetics. Condensation onto stepped surfaces demonstrates preferred bonding and nucleation at step edges. Detailed studies of potassium incorporation in crystalline C(60) show highly ordered structures in the K(3)C(60) metallic state but disordered non-metallic structures for high potassium concentrations.     

Real-space imaging of two-dimensional antiferromagnetism on the atomic scale

A two-dimensional antiferromagnetic structure within a pseudomorphic monolayer film of chemically identical manganese atoms on tungsten(110) was observed with atomic resolution by spin-polarized scanning tunneling microscopy at 16 kelvin. A magnetic superstructure changes the translational symmetry of the surface lattice with respect to the chemical unit cell. It is shown, with the aid of first-principles calculations, that as a result of this, spin-polarized tunneling electrons give rise to an image corresponding to the magnetic superstructure and not to the chemical unit cell. These investigations demonstrate a powerful technique for the understanding of complicated magnetic configurations of nanomagnets and thin films engineered from ferromagnetic and antiferromagnetic materials used for magnetoelectronics.     

Topologically linked protein rings in the bacteriophage HK97 capsid

The crystal structure of the double-stranded DNA bacteriophage HK97 mature empty capsid was determined at 3.6 angstrom resolution. The 660 angstrom diameter icosahedral particle contains 420 subunits with a new fold. The final capsid maturation step is an autocatalytic reaction that creates 420 isopeptide bonds between proteins. Each subunit is joined to two of its neighbors by ligation of the side-chain lysine 169 to asparagine 356. This generates 12 pentameric and 60 hexameric rings of covalently joined subunits that loop through each other, creating protein chainmail: topologically linked protein catenanes arranged with icosahedral symmetry. Catenanes have not been previously observed in proteins and provide a stabilization mechanism for the very thin HK97 capsid.     

Subunit structure of aldolase

A new crystal form of rabbit muscle aldolase shows that the molecule has 222 symmetry to at least 4-angstrom resolution, and hence that the gross conformation of the four subunits is the same. Comparison of the new form with a previously reported form establishes the number of molecules per unit cell, n, in the older form. For an independent check, the "crystal-volume and protein-content method" was developed to determine n without directly measuring the water content of the crystals.     

Orientational and Magnetic Ordering of Buckyballs in TDAE-C60

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.     

Single-bond formation and characterization with a scanning tunneling microscope

A scanning tunneling microscope (STM) was used to manipulate the bonding of a carbon monoxide (CO) molecule and to analyze the structure and vibrational properties of individual products. Individual iron (Fe) atoms were evaporated and coadsorbed with CO molecules on a silver (110) surface at 13 kelvin. A CO molecule was transferred from the surface to the STM tip and bonded with an Fe atom to form Fe(CO). A second CO molecule was similarly transferred and bonded with Fe(CO) to form Fe(CO)(2). Controlled bond formation and characterization at the single-bond level probe chemistry at the spatial limit.