Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.

https://science.sciencemag.org/content/sci/258/5087/1474.full.pdf

Photoinduced electron transfer from a conducting polymer to buckminsterfullerene.

Preface Acknowledgements Notation Part I. Overview and Background Topics: 1. Introduction 2. Overview 3. Theoretical background 4. Periodic solids and electron bands 5. Uniform electron gas and simple metals Part II. Density Functional Theory: 6. Density functional theory: foundations 7. The Kohn-Sham ansatz 8. Functionals for exchange and correlation 9. Solving the Kohn-Sham equations Part III. Important Preliminaries on Atoms: 10. Electronic structure of atoms 11. Pseudopotentials Part IV. Determination of Electronic Structure, The Three Basic Methods: 12. Plane waves and grids: basics 13. Plane waves and grids: full calculations 14. Localized orbitals: tight binding 15. Localized orbitals: full calculations 16. Augmented functions: APW, KKR, MTO 17. Augmented functions: linear methods Part V. Predicting Properties of Matter from Electronic Structure - Recent Developments: 18. Quantum molecular dynamics (QMD) 19. Response functions: photons, magnons ... 20. Excitation spectra and optical properties 21. Wannier functions 22. Polarization, localization and Berry's phases 23. Locality and linear scaling O (N) methods 24. Where to find more Appendixes References Index.

Electronic Structure: Basic Theory and Practical Methods

THE synthesis of macroscopic amounts of C60 and C70 (fullerenes)1 has stimulated a variety of studies on their chemical and physical properties2,3. We recently demonstrated that C60 and C70 become conductive when doped with alkali metals4. Here we describe low-temperature studies of potassium-doped C60 both as films and bulk samples, and demonstrate that this material becomes superconducting. Superconductivity is demonstrated by microwave, resistivity and Meissner-effect measurements. Both polycrystalline powders and thin-film samples were studied. A thin film showed a resistance transition with an onset temperature of 16 K and essentially zero resistance near 5 K. Bulk samples showed a well-defined Meissner effect and magnetic-field-dependent microwave absorption beginning at 18 K. The onset of superconductivity at 18 K is the highest yet observed for a molecular superconductor.

/pdf/superconductivity-at-18-k-in-potassium-doped-c60-30fq0lzflp.pdf

Superconductivity at 18 K in potassium-doped C60

Inorganic sheets: Graphene-like MoS2 and WS2 were prepared by three different chemical methods. Examination by microscopic techniques revealed that they consist of one or a few layers (see depicted TEM image of WS2 layers), and an atomic-resolution TEM image showed that layered MoS2 has a hexagonal arrangement of Mo and S atoms (see inset).

MoS2 and WS2 Analogues of Graphene

In this Account we highlight the experimental evidence in favor of our view that carbon nanotubes should be considered as a new macromolecular form of carbon with unique properties and with great potential for practical applications. We show that carbon nanotubes may take on properties that are normally associated with molecular species, such as solubility in organic solvents, solution-based chemical transformations, chromatography, and spectroscopy. It is already clear that the nascent field of nanotube chemistry will rival that of the fullerenes.

Chemistry of single-walled carbon nanotubes.

We have prepared and identified as a single phase the high-temperature superconducting compound in the chemical system Y-Ba-Cu-O, an orthorhombic, distorted oxygen-deficient perovskite of stoichiometry ${\mathrm{Ba}}_{2}$${\mathrm{YCu}}_{3}$${\mathrm{O}}_{9\mathrm{\ensuremath{-}}\mathrm{\ensuremath{\delta}}}$ (\ensuremath{\delta}\ensuremath{\simeq}2.1). Samples exhibit zero resistance at 91 K, with a transition width of 1.5 K. The Meissner effect attains a value of 76% of the independently measured diamagnetic susceptibility. We estimate parameters that characterize this superconductor, e.g., \ensuremath{\gamma}\ensuremath{\simeq}3--5 mJ (mole Cu${)}^{\mathrm{\ensuremath{-}}1}$ ${\mathrm{K}}^{\mathrm{\ensuremath{-}}2}$. The critical current density at 77 K and H=0 exceeds 1100 A/${\mathrm{cm}}^{2}$.

https://link.aps.org/pdf/10.1103/PhysRevLett.58.1676

Bulk superconductivity at 91 K in single-phase oxygen-deficient perovskite Ba 2 YCu 3 O 9 − δ

THE recent syntheses1,2 of macroscopic quantities of C60 have suggested possible applications in host–guest and organic chemistry, tribology, electrochemistry and semiconductor tech-nology. Here we report the preparation of alkali-metal-doped films of C60 and C70 which have electrical conductivities at room temperature that are comparable to those attained by n-type doped polyacetylene. The highest conductivities observed in the doped films are: 4Scm−1 (Cs/C60), 100 (Rb/C60), 500 (K/C60), 20 (Na/C60), 10 (Li/C60), 2 (K/C70). The doping process is reversed on exposure of the films to the atmosphere. At high doping levels, the films become more resistive. We attribute the conductivity induced in these films to the formation of energy bands from the π orbitals of C60 or C70, which become partially filled with carriers on doping. The smaller alkali metal ions should be able to fit into the interstices in the lattice without disrupting the network of contacts between the carbon spheroids. In the case of C60, this would allow the development of an isotropic band structure, and we therefore propose that these materials may constitute the first three-dimensional 'organic' conductors.

Conducting films of C60 and C70 by alkali-metal doping

Meissner-effect and microwave-absorption measurements on bulk samples show that ${\mathrm{Rb}}_{\mathit{x}}$${\mathrm{C}}_{60}$ is superconducting with a maximum transition temperature of 28 K. This is a 10-K (60%) increase over the K-doped material. Only ${\mathrm{Ba}}_{0.6}$${\mathrm{K}}_{0.4}$${\mathrm{BiO}}_{3}$ and the cuprate superconductors have higher transition temperatures.

/pdf/superconductivity-at-28-k-in-rbxc60-3bdevp5dh5.pdf

Superconductivity at 28 K in RbxC60.

Single crystal sof the 84-K superconductor ${\mathrm{Bi}}_{2.2}{\mathrm{Sr}}_{2}{\mathrm{Ca}}_{0.8}{\mathrm{Cu}}_{2}{\mathrm{O}}_{8+\ensuremath{\delta}}$ were characterized by x-ray diffraction, dc magnetic susceptibility, electrical resistivity, and microwave absorption. The structure has ${[\mathrm{Cu}{\mathrm{O}}_{2}]}_{\ensuremath{\infty}}$ planes separated by calcium atoms, edge-shared bismuth oxide double layers, and an incommensurate superlattice along $b$ with a period of 4.76. The in-plane resistivity above ${T}_{c}$ is linear in $T$, with ${\ensuremath{\rho}}_{\mathrm{RT}}=130$ \ensuremath{\mu}\ensuremath{\Omega} cm. Initial results on Pb substitution yielding ${T}_{c}'\mathrm{s}$ of 107 K are reported.

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

THE discovery of conductivity1 in AxC60 (where A represents an alkali metal) and superconductivity2 in KxC60 has been followed by reports of superconductivity in other alkali-metal-doped full-erides with transition temperatures as high as 33 K (ref. 3). Elucidation of phase diagrams and understanding the relationship between structure and superconducting properties is essential to a detailed understanding of superconductivity in these systems. So far, structural data have been reported only for the non-conducting, intercalated body-centred cubic (b.c.c.) structures A6C60 (where A is K or Cs; ref. 4), a body-centred tetragonal structure for A6C60 (where A is K, Rb, Cs; ref. 5) and the superconducting, intercalated face-centred cubic (f.c.c.) material K3C60 (ref. 6). Here we report the preparation of a series of single-phase, isostructural f.c.c. superconductors with composition A3C60 (where A is K, Rb, Cs or a mixture of these), and show that Tcc increases monotonically with the size of the unit cell. Extended Hiickel band-structure calcula-tions also show a monotonic increase in the density of states at the Fermi level, N(EF), with lattice parameter. The primary impli-cation of these results is that all A3C60 superconductors have the same structure and that changes in Tc can be accounted for by changes in N(EF).

S. M. Zahurak

Papers

Bulk superconductivity at 91 K in single-phase oxygen-deficient perovskite Ba 2 YCu 3 O 9 − δ

Conducting films of C60 and C70 by alkali-metal doping

Superconductivity at 28 K in RbxC60.

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

Relation of structure and superconducting transition temperatures in A3C60