257 research outputs found
Electronic structure of barium-doped C<sub>60</sub>
We have investigated the electronic structure of Ba-doped C60 films with Ba concentrations of up to x≈12 (BaxC60) by applying valence-band photoemission and x-ray-absorption spectroscopy. A crystal orbital (CO) formalism based on a semiempirical Hamiltonian of the intermediate-neglect-of-differential-overlap type has been employed to derive solid-state results for the Ba-doped C60 fullerides. Using x-ray diffraction, we show three distinct phases for the bulk BaxC60 system with Ba concentrations of up to x=6. In all cases, the experimental observations strongly indicate that fulleride formation leads to the occupation of hybrid bands on both sides of the Fermi level. The theoretical data indicate that the alkaline-earth atoms are essentially monovalent and hybridize strongly with the π-type functions of the C60 network. The Ba atoms in the BaxC60 fullerides deviate from the limit of complete charge transfer as a consequence of the competition between covalent Ba-C60 bonding and ionic contributions. Furthermore, it is shown that the calculated density-of-state profiles reproduce the photoemission data in the extreme outer valence-band region
Electronic Structure of the C<sub>60</sub> Fragment in Alkali- and Alkaline-earth-doped Fullerides
The electronic structure of the C60 fragment in alkali- and alkaline-earth-doped fullerides is studied theoretically. With increasing metal-to-C60 charge transfer (CT) the n electronic properties of the soccerball are changed. In the undoped solid and for not too high a concentration of doping atoms the hexagon-hexagon (6-6) bonds show sizeable double bond character while the hexagon-pentagon (6-5) bonds are essentially of single bond type. In systems with a high concentration of doping atoms this relative ordering is changed. Now the 6-5 bonds have partial double bond character and the 6-6 bonds are essentially single bonds. The high ability of the C60 unit to accomodate excess electrons prevents any sizeable weakening of the overall n bonding in systems with up to 12 excess electrons on the soccerball. A crystal orbital (CO) formalism on the basis of an INDO (intermediate neglect of differential overlap) Hamiltonian has been employed to derive solid state results for potassium- and barium-doped C60 fullerides. For both types of doping atoms an incomplete metal-to-C60 CT is predicted. In the potassium-doped fullerides the magnitude of the CT depends on the interstitial site of the dopant. The solid state data have been supplemented by INDO and ab initio calculations on molecular C60, C6-60 and C12-60. The calculated bondlength alternation in the neutral molecule is changed in C12-60 where the length of the 6-6 bonds exceeds the length of the 6-5 bonds. The geometries of the three molecular species have been optimized with a 3-21 G* basis. The theoretically derived modification of the C60 (π) electronic structure as a function of the electron count is explained microscopically in the framework of two quantum statistics accessible for π electronic ensembles. In the π ensemble of the C60 fragment so-called hard core bosonic properties are maximized where the Pauli antisymmetry principle has the character of a hidden variable only. Here the electronic degrees of freedom are attenuated only by the Pauli exclusion principle. This behaviour leads to the changes in the π electronic structure mentioned above
Sustained Water Oxidation by Direct Electrosynthesis of Ultrathin Organic Protection Films on Silicon
Artificial photosynthesis allows exceeding the efficiency and stability limits of natural photosynthesis. Based on the use of semiconducting absorbers, high efficiency in water photolysis has been achieved in various photoelectrode configurations. However, integrated systems are limited in their stability, and more stable half-cell electrodes use protection films prepared by laborious methods. Herein, the facile low-temperature preparation of ultrathin organic protection coatings is demonstrated. The formation is based on the catalytic properties of water oxidation catalysts toward alcohol-polymerization reactions, which results in the formation of hitherto unknown protection layers on silicon. The interfacial layers are generated via iodine-mediated electro-reductive polymerization of ethanol, concomitantly forming during electrophoretic transport of RuO_2 onto silicon supports. Reaction chemistry analyses show that the RuO_2-induced catalysis introduces E2-elimination reactions which result in a carbon sp^3 –sp^2 transformation of the film. For the two modes of photoelectrochemical operation, the photovoltaic and the photoelectrocatalytic mode, 20 and 15 mA cm^(−2) photocurrent densities, respectively, are obtained with unaltered output for 8 and 24 h. The interfacial layer enables Si photovoltages of 500 mV, demonstrating extraordinary electronic interface quality. Since only hydrogen termination of the surface is a prerequisite for growth of the organic protection layer, the method is applicable to a wide range of semiconductors
Structure and properties of a novel fulleride Sm6C60
A novel fulleride Sm6C60 has been synthesized using high temperature solid
state reaction. The Rietveld refinement on high resolution synchrotron X-ray
powder diffraction data shows that Sm6C60 is isostructural with body-centered
cubic A6C60 (A=K, Ba). Raman spectrum of Sm6C60 is similar to that of Ba6C60,
and the frequencies of two Ag modes in Sm6C60 are nearly the same as that of
Ba6C60, suggesting that Sm is divalent and hybridization between C60 molecules
and the Sm atom could exist in Sm6C60. Resistivity measurement shows a weak
T-linear behavior above 180 K, the transport at low temperature is mainly
dominated by granular-metal theory.Comment: 9 pages, 3 figures, submitted to Phys. Rev. B (March 12, 1999
Orbital character of O 2p unoccupied states near the Fermi level in CrO2
The orbital character, orientation, and magnetic polarization of the O 2
unoccupied states near the Fermi level () in CrO was determined using
polarization-dependent X-ray absorption spectroscopy (XAS) and X-ray magnetic
circular dichroism (XMCD) from high-quality, single-crystal films. A sharp peak
observed just above is excited only by the electric field vector () normal to the tetragonal -axis, characteristic of a narrow band
( 0.7 eV bandwidth) constituted from O 2 orbitals perpendicular to
(O 2) hybridized with Cr 3 states. By comparison
with band-structure and configuration-interaction (CI) cluster calculations our
results support a model of CrO as a half-metallic ferromagnet with large
exchange-splitting energy ( 3.0 eV) and
substantial correlation effects.Comment: 4 pages, 3 figures, accepted for publication in Phys. Rev. B Rapid
Com
Sub-surface Oxygen and Surface Oxide Formation at Ag(111): A Density-functional Theory Investigation
To help provide insight into the remarkable catalytic behavior of the
oxygen/silver system for heterogeneous oxidation reactions, purely sub-surface
oxygen, and structures involving both on-surface and sub-surface oxygen, as
well as oxide-like structures at the Ag(111) surface have been studied for a
wide range of coverages and adsorption sites using density-functional theory.
Adsorption on the surface in fcc sites is energetically favorable for low
coverages, while for higher coverage a thin surface-oxide structure is
energetically favorable. This structure has been proposed to correspond to the
experimentally observed (4x4) phase. With increasing O concentrations, thicker
oxide-like structures resembling compressed Ag2O(111) surfaces are
energetically favored. Due to the relatively low thermal stability of these
structures, and the very low sticking probability of O2 at Ag(111), their
formation and observation may require the use of atomic oxygen (or ozone, O3)
and low temperatures. We also investigate diffusion of O into the sub-surface
region at low coverage (0.11 ML), and the effect of surface Ag vacancies in the
adsorption of atomic oxygen and ozone-like species. The present studies,
together with our earlier investigations of on-surface and
surface-substitutional adsorption, provide a comprehensive picture of the
behavior and chemical nature of the interaction of oxygen and Ag(111), as well
as of the initial stages of oxide formation.Comment: 17 pages including 14 figures, Related publications can be found at
http://www.fhi-berlin.mpg.de/th/paper.htm
Neurotized Free Muscle Flaps can Produce MRI Changes Mimicking Tumour Recurrence
Soft tissue sarcomas are investigated by magnetic resonance imaging (MRI) both for initial staging and follow-up. We
describe the presence of increased signal on T2-weighted images caused by a neurotized muscle flap following reconstructive
surgery. This raised concern about possible sarcoma recurrence that was not clinically evident. On post-operative imaging
of sarcomas the presence of recurrent tumour is indicated by a mass and high signal intensity on T2-weighted images.
However, high signal changes in skeletal muscle on T2-weighted images are not specific. In this case, the free functioning
muscle transfer with neurotization of the flap mimicked recurrence on MR scan. High signal intensity on T2-weighted
images in muscle is an indication of either a physiological change or a pathological condition and must be taken in
context of the clinical picture
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