First-principles electronic structure of spinelLiCr2O4:A possible half-metal

We have employed first-principles electronic structure calculations to examine the hypothetical (but plausible) oxide spinel, ${\mathrm{LiCr}}_{2}{\mathrm{O}}_{4}$ with the ${d}^{2.5}$ electronic configuration. The cell (cubic) and internal (oxygen position) structural parameters have been obtained for this compound through structural relaxation in the first-principles framework. Within the one-electron band picture, we find that ${\mathrm{LiCr}}_{2}{\mathrm{O}}_{4}$ is magnetic, and a candidate half-metal. The electronic structure is substantially different from the closely related and well-known rutile half-metal ${\mathrm{CrO}}_{2}.$ In particular, we find a smaller conduction-band width…

Evidence for eight node mixed-symmetry superconductivity in a correlated organic metal

We report a combined theoretical and experimental investigation of the superconducting state in the quasi-two-dimensional organic superconductor $\kappa$-(ET)$_2$Cu[N(CN)$_2$]Br. Applying spin-fluctuation theory to a low-energy material-specific Hamiltonian derived from ab initio density functional theory we calculate the quasiparticle density of states in the superconducting state. We find a distinct three-peak structure that results from a strongly anisotropic mixed-symmetry superconducting gap with eight nodes and twofold rotational symmetry. This theoretical prediction is supported by low-temperature scanning tunneling spectroscopy on in situ cleaved single crystals of $\kappa$-(ET)$_2$…

Electronic structure of the spin-12quantum magnet TiOCl

We have studied the electronic structure of the spin-$1∕2$ quantum magnet TiOCl by polarization-dependent momentum-resolved photoelectron spectroscopy. From that, we confirm the quasi-one-dimensional nature of the electronic structure along the crystallographic $b$ axis and find no evidence for sizable phonon-induced orbital fluctuations as the origin for the noncanonical phenomenology of the spin-Peierls transition in this compound. A comparison of the experimental data to our own $\mathrm{LDA}+\mathrm{U}$ and Hubbard model calculations reveals a striking lack of understanding regarding the quasi-one-dimensional electron dispersions in the normal state of this compound.

Microscopic origin of the charge transfer in single crystals based on thiophene derivatives: A combined NEXAFS and density functional theory approach

We have investigated the charge transfer mechanism in single crystals of DTBDT-TCNQ and DTBDT-F4TCNQ (where DTBDT is dithieno[2,3-d;2',3'-d'] benzo[1,2-b;4,5-b']dithiophene) using a combination of near-edge X-ray absorption spectroscopy (NEXAFS) and density functional theory calculations (DFT) including final state effects beyond the sudden state approximation. In particular, we find that a description that considers the partial screening of the electron-hole Coulomb correlation on a static level as well as the rearrangement of electronic density shows excellent agreement with experiment and allows to uncover the details of the charge transfer mechanism in DTBDT-TCNQ and DTBDT-F4 TCNQ, as w…

Orbital-Resolved Partial Charge Transfer from the Methoxy Groups of Substituted Pyrenes in Complexes with Tetracyanoquinodimethane—A NEXAFS Study

It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds and their electronic properties. Microcrystals of tetra-/hexamethoxypyrene as donors with the strong acceptor tetracyano-p-quinodimethane (TMP/HMP-TCNQ) were grown by vapor diffusion. The oxygen and nitrogen K-edge spectra are spectroscopic fingerprints of the functional groups in the donor and acceptor moieties, respectively. The orbital selectivity of the NEXAFS pre-edge resonances allows us to precisely elucidate the participation of specific orbitals in the charge transfer process. Upon complex formation, the intensit…

Electronic structure studies ofBaFe2As2by angle-resolved photoemission spectroscopy

We report high resolution angle-resolved photoemission spectroscopy (ARPES) studies of the electronic structure of ${\text{BaFe}}_{2}{\text{As}}_{2}$, which is one of the parent compounds of the Fe-pnictide superconductors. ARPES measurements have been performed at 20 and 300 K, corresponding to the orthorhombic antiferromagnetic phase and the tetragonal paramagnetic phase, respectively. Photon energies between 30 and 175 eV and polarizations parallel and perpendicular to the scattering plane have been used. Measurements of the Fermi surface yield two hole pockets at the $\ensuremath{\Gamma}$ point and an electron pocket at each of the $X$ points. The topology of the pockets has been conclu…

Investigation of Many‐Body Effects in the Quasi‐Two‐Dimensional Electronic System of Organic Charge‐Transfer Salts

Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…

Orbital character variation of the Fermi surface and doping dependent changes of the dimensionality inBaFe2−xCoxAs2from angle-resolved photoemission spectroscopy

From a combination of high resolution angle-resolved photoemission spectroscopy and density functional calculations, we derive information on the dimensionality and the orbital character of the electronic states of ${\text{BaFe}}_{2\ensuremath{-}x}{\text{Co}}_{x}{\text{As}}_{2}$. Upon increasing Co doping, the electronic states in the vicinity of the Fermi level take on increasingly three-dimensional character. Both the orbital variation with ${k}_{z}$ and the more three-dimensional nature of the doped compounds have important consequences for the nesting conditions and thus possibly also for the appearance of antiferromagnetic and superconducting phases.

CCDC 1817871: Experimental Crystal Structure Determination

Related Article: Manuel Souto, Maria Chiara Gullo, HengBo Cui, Nicola Casati, Fabio Montisci, Harald O. Jeschke, Roser Valentí, Imma Ratera, Concepció Rovira, Jaume Veciana|2018|Chem.-Eur.J.|24|5500|doi:10.1002/chem.201800881

CCDC 1817872: Experimental Crystal Structure Determination

Related Article: Manuel Souto, Maria Chiara Gullo, HengBo Cui, Nicola Casati, Fabio Montisci, Harald O. Jeschke, Roser Valentí, Imma Ratera, Concepció Rovira, Jaume Veciana|2018|Chem.-Eur.J.|24|5500|doi:10.1002/chem.201800881