Unusual polymerization in the Li4C60 fulleride

Li4C60, one of the best representatives of lithium intercalated fullerides, features a novel type of 2D polymerization. Extensive investigations, including laboratory x-ray and synchrotron radiation diffraction, 13C NMR, MAS and Raman spectroscopy, show a monoclinic I2/m structure, characterized by chains of [2+2]-cycloaddicted fullerenes, sideways connected by single C-C bonds. This leads to the formation of polymeric layers, whose insulating nature, deduced from the NMR and Raman spectra, denotes the complete localization of the electrons involved in the covalent bonds.Comment: 7 pages, 6 figures, RevTex4, submitted to Phys. Rev.

Recovering Metallicity in A4C60: The Case of Monomeric Li4C60

The restoration of metallicity in the high-temperature, cubic phase of Li4C60 represents a remarkable feature for a member of the A4C60 family (A = alkali metal), invariably found to be insulators. Structural and resonance technique investigations on Li4C60 at T > 600 K, show that its fcc structure is associated with a complete (4e) charge transfer to C60 and a sparsely populated Fermi level. These findings not only emphasize the crucial role played by lattice symmetry in fulleride transport properties, but also re-dimension the role of Jahn-Teller effects in band structure determination. Moreover, they suggest the present system as a potential precursor to a new class of superconducting fullerides.Comment: 4 pages, 3 figure

Interactive effects between carbon allotrope fillers on the mechanical reinforcement of polyisoprene based nanocomposites

Interactive effects of carbon allotropes on the mechanical reinforcement of polymer nanocomposites were investigated. Carbon nanotubes (CNT) and nano-graphite with high shape anisotropy (nanoG) were melt blended with poly(1,4- cis-isoprene), as the only fillers or in combination with carbon black (CB), measuring the shear modulus at low strain amplitudes for peroxide crosslinked composites. The nanofiller was found to increase the low amplitude storage modulus of the matrix, with or without CB, by a factor depending on nanofiller type and content. This factor, fingerprint of the nanofiller, was higher for CNT than for nanoG. The filler-polymer interfacial area was able to correlate modulus data of composites with CNT, CB and with the hybrid filler system, leading to the construction of a common master curve. © BME-PT

Absence of giant spin splitting in the two-dimensional electron liquid at the surface of SrTiO3 (001)

We reinvestigate the putative giant spin splitting at the surface of SrTiO3 reported by Santander-Syro et al. [Nature Mat. 13, 1085 (2014)]. Our spin- and angle-resolved photoemission experiments on fractured (001) oriented surfaces supporting a two-dimensional electron liquid with high carrier density show no detectable spin polarization in the photocurrent. We demonstrate that this result excludes a giant spin splitting while it is consistent with the unconventional Rashba-like splitting seen in band structure calculations that reproduce the experimentally observed ladder of quantum confined subbands.PostprintPeer reviewe

Persistence of antiferromagnetic order upon La substitution in the 4d44d^4 Mott insulator Ca2_2RuO4_4

The chemical and magnetic structures of the series of compounds Ca$_{2-x}$La$_x$RuO$_4$ [$x = 0$, $0.05(1)$, $0.07(1)$, $0.12(1)$] have been investigated using neutron diffraction and resonant elastic x-ray scattering. Upon La doping, the low temperature S-Pbca space group of the parent compound is retained in all insulating samples [$x\leq0.07(1)$], but with significant changes to the atomic positions within the unit cell. These changes can be characterised in terms of the local RuO$_6$ octahedral coordination: with increasing doping the structure, crudely speaking, evolves from an orthorhombic unit cell with compressed octahedra to a quasi-tetragonal unit cell with elongated ones. The magnetic structure on the other hand, is found to be robust, with the basic $k=(0,0,0)$, $b$-axis antiferromagnetic order of the parent compound preserved below the critical La doping concentration of $x\approx0.11$. The only effects of La doping on the magnetic structure are to suppress the A-centred mode, favouring the B mode instead, and to reduce the N\'{e}el temperature somewhat. Our results are discussed with reference to previous experimental reports on the effects of cation substitution on the $d^4$ Mott insulator Ca$_2$RuO$_4$, as well as with regard to theoretical studies on the evolution of its electronic and magnetic structure. In particular, our results rule out the presence of a proposed ferromagnetic phase, and suggest that the structural effects associated with La substitution play an important role in the physics of the system.Comment: 10 pages, 9 figure

An optically stimulated superconducting-like phase in K3C60 far above equilibrium Tc

The control of non-equilibrium phenomena in complex solids is an important research frontier, encompassing new effects like light induced superconductivity. Here, we show that coherent optical excitation of molecular vibrations in the organic conductor K3C60 can induce a non-equilibrium state with the optical properties of a superconductor. A transient gap in the real part of the optical conductivity and a low-frequency divergence of the imaginary part are measured for base temperatures far above equilibrium Tc=20 K. These findings underscore the role of coherent light fields in inducing emergent order.Comment: 40 pages, 23 figure

The structural and electronic evolution of Li4C60 through the polymer–monomer transformation

In this paper, we combine synchrotron powder x-ray diffraction, 7Li nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) experiments to study the structural evolution of Li4C60 and how its electronic ground state depends on the crystal symmetry. The compound in the two-dimensional polymer phase with mixed interfullerene bonding motifs is a band gap insulator. EPR, however, reveals the presence of intrinsic centers originating from broken C60–C60 bonds and local Li off-stoichiometry that create states in the band gap and account for the complex temperature dependence of the spin susceptibility as well as the residual temperature dependence of the 7Li NMR shift. At low temperatures, the Li+ ions are statically disordered on the 7Li NMR timescale. The observed 7Li NMR line narrowing at T>200 K is ascribed to the Li+ diffusion dynamics and above room temperature the polymer phase is already a good ionic conductor. Heating the sample to temperatures above ~470 K results in gradual depolymerization to the metallic monomer fcc high temperature structure. The transformation is first order and polymer as well as monomer phases coexist over a broad temperature interval (130 K)

Observation of Large Topologically Trivial Fermi-Arcs in the Candidate Type-II Weyl Semimetal WTe2

We report angle-resolved photoemission experiments resolving the distinct electronic structure of the inequivalent top and bottom (001) surfaces of WTe2. On both surfaces, we identify a surface state that forms a large Fermi-arc emerging out of the bulk electron pocket. Using surface electronic structure calculations, we show that these Fermi arcs are topologically trivial and that their existence is independent of the presence of type-II Weyl points in the bulk band structure. This implies that the observation of surface Fermi arcs alone does not allow the identification of WTe2 as a topological Weyl semimetal. We further use the identification of the two different surfaces to clarify the number of Fermi surface sheets in WTe2.Comment: Accepted in Physical Review B Rapid Communication on 16 Aug 201

In situ strain tuning of the metal-insulator-transition of Ca2RuO4 in angle-resolved photoemission experiments

Pressure plays a key role in the study of quantum materials. Its application in angle resolved photoemission (ARPES) studies, however, has so far been limited. Here, we report the evolution of the k-space electronic structure of bulk Ca2RuO4, lightly doped with Pr, under uniaxial strain. Using ultrathin plate-like crystals, we achieve uniaxial strain levels up to -4.1%, sufficient to suppress the insulating Mott phase and access the previously unexplored electronic structure of the metallic state at low temperature. ARPES experiments performed while tuning the uniaxial strain reveal that metallicity emerges from a marked redistribution of charge within the Ru t2g shell, accompanied by a sudden collapse of the spectral weight in the lower Hubbard band and the emergence of a well-defined Fermi surface which is devoid of pseudogaps. Our results highlight the profound roles of lattice energetics and of the multiorbital nature of Ca2RuO4 in this archetypal Mott transition and open new perspectives for spectroscopic measurements