Toroidal dipolar response in a metamaterial

Toroidal multipoles are fundamental electromagnetic excitations different from those associated with the familiar charge and magnetic multipoles. They have been held responsible for parity violation in nuclear and particle physics, but direct evidence of their existence in classical electrodynamics has remained elusive. We report on the observation of a resonant electromagnetic response in an artificially engineered medium, or metamaterial, that cannot be attributed to magnetic or charge multipoles and can only be explained by the existence of a toroidal dipole. Our direct experimental evidence of the toroidal response brings attention to the often ignored electromagnetic interactions involving toroidal multipoles, which could be present in naturally occurring systems, especially at the macromolecule level, where toroidal symmetry is ubiquitous.     

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.     

Radical reactions of c60

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.     

Compressibility of solid c60

Room-temperature powder x-ray diffraction profiles have been obtained at hydrostatic pressures P = 0 and 1.2 gigapascals on the solid phase of cubic C(60) ("fullerite"). Within experimental error, the linear compressibility d(ln a)/dP is the same as the interlayer compressibility d(ln c)/dP of hexagonal graphite, consistent with van der Waals intermolecular bonding. The volume compressibility -d(ln V)/dP is 7.0 +/- 1 x 10(-12) square centimeter per dyne, 3 and 40 times the values for graphite and diamond, respectively.     

Ring currents in icosahedral c60

A new formulation of the current within the London approximation allows the calculation of ring currents in topologically complex molecules. Application of this theory to C(60) demonstrates the existence of remarkable pi electron ring currents. Paramagnetic currents, in size comparable to the ones in benzene, flow within the pentagons, whereas weaker diamagnetic currents flow all around the C.(60) molecule. The overall vanishing ring-current magnetic susceptibility results from a cancellation of diamagnetic and paramagnetic contributions. The presence of ring currents significantly affects chemical shifts as measured in nuclear magnetic resonance experiments. In contrast to the magnetic susceptibility, which is a property of the molecule as a whole, chemical shifts are sensitive to the local magnetic field and the effect of ring currents does not vanish.     

An orientational transition of bent-core molecules in an anisotropic matrix

We report the discovery of an orientational transition of bent-core molecules in a background anisotropic medium, in this case a smectic liquid crystal made of rod-like molecules. The resulting director is apolar in nature, and the medium can be described as an orthogonal biaxial smectic. The detailed phase diagram of mixtures of the two types of compounds revealed the induction of two liquid crystalline phases that are specific to compounds with bent-core molecules. The chemical nature of the bounding surface had a marked influence on the observed textures.     

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.     

Direct fabrication of large micropatterned single crystals

Micropatterning of single crystals for technological applications is a complex, multistep process. Nature provides alternative fabrication strategies, when crystals with exquisite micro-ornamentation directly develop within preorganized frameworks. We report a bio-inspired approach to growing large micropatterned single crystals. Micropatterned templates organically modified to induce the formation of metastable amorphous calcium carbonate were imprinted with calcite nucleation sites. The template-directed deposition and crystallization of the amorphous phase resulted in the fabrication of millimeter-sized single calcite crystals with sub-10-micron patterns and controlled crystallographic orientation. We suggest that in addition to regulating the shape, micropatterned frameworks act as sites for stress and impurity release during the amorphous-to-crystalline transition. The proposed mechanisms may have direct biological relevance and broad implications in materials synthesis.     

Systematic inflation of buckminsterfillerene c60: synthesis of diphenyl fulleroids c61 to c66

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.     

Sex differences in electric signaling in an electric fish

The electric discharge of Sternopygus macrurus is distinctly different from the discharges of ten sympatric species of electric fish in Guyana, South America. Sternopygus is the first known example of a fish with sexually different electric discharges. Males and females differ in the steady-state frequency of their discharges, and males produce variations in their discharge during courtship. Playback experiments demonstrate that species and sex differences in electric discharges have communicative significance.     

Organic molecular soft ferromagnetism in a fullerene c60

The properties of an organic molecular ferromagnet [C(60)TDAE(0.86); TDAE is tetrakis(dimethylamino)ethylene] with a Curie temperature ;T(c) = 16.1 kelvin are described. The ferromagnetic state shows no remanence, and the temperature dependence of the magnetization below ;T(c) does not follow the behavior expected of a conventional ferromagnet. These results are interpreted as a reflection of a three-dimensional system leading to a soft ferromagnet.     

Fabrication and properties of free-standing c60 membranes

Van der Waals forces that bind C(60) molecular solids are found to be sufficiently strong to allow the reproducible fabrication of free-standing C(60) membranes on (100) silicon wafers. Membranes, 2000 to 6000 angstroms thick, were fabricated by a modified silicon micro-machining process and were found to be smooth, flat, and mechanically robust. An important aspect of the silicon-compatible fabrication procedure is the demonstration that C(60) films can be uniformly and nondestructively thinned in a CF(4) plasma. Young's modulus and fracture strength measurements were made on membranes with areas larger than 6 millimeters by 6 millimeters. It may be possible to use C(60), membranes for physical property measurements and applications.     

Synthetic zeolites: growth of larger single crystals

Synthetic zeolites 4A, P, and X were grown in acrylic gel to a size suitable for study of single crystals by x-ray diffraction.     

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.     

Controlling factors for the brittle-to-ductile transition in tungsten single crystals

Materials performance in structural applications is often restricted by a transition from ductile response to brittle fracture with decreasing temperature. This transition is currently viewed as being controlled either by dislocation mobility or by the nucleation of dislocations. Fracture experiments on tungsten single crystals reported here provide evidence for the importance of dislocation nucleation for the fracture toughness in the semibrittle regime. However, it is shown that the transition itself, in general, is controlled by dislocation mobility rather than by nucleation.     

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.     

Controlled atomic doping of a single C60 molecule

We report a method for controllably attaching an arbitrary number of charge dopant atoms directly to a single, isolated molecule. Charge-donating K atoms adsorbed on a silver surface were reversibly attached to a C60 molecule by moving it over K atoms with a scanning tunneling microscope tip. Spectroscopic measurements reveal that each attached K atom donates a constant amount of charge (approximately 0.6 electron charge) to the C60 host, thereby enabling its molecular electronic structure to be precisely and reversibly tuned.     

Collapse of gels in an electric field

An infinitesimal change in electric potential across a polyelectrolyte gel produces a discrete, reversible volume change. The volume of the collapsed gel can be several hundred times smaller than that of the swollen gel.     

Unconditioned response to electric shock: mechanism in planarians

Some implications of a mathematical theory relating neuronal geometry to the parameters of excitation in unconditioned response of planarians to electric shock are experimentally verified. The regions and patterns of primary neural excitation depend on the relation between the distribution of neural sizes and the wave form of the electric stimulus.