167,304 research outputs found
Transition metal decorated soft nanomaterials through modular self-assembly of an asymmetric hybrid polyoxometalate
An asymmetrically functionalised Wells–Dawson organic–inorganic hybrid polyoxometalate has been post-functionalised by Pt2+ coordination, and demonstrates self-assembly into surface-decorated micellar nanostructures. This multifunctional hybrid material is found to be a redox-active soft nanomaterial and demonstrates a new molecular design strategy with potential for applications in photo- or electro-catalysis
White Lines and 3d-Occupancy for the 3d Transition-Metal Oxides
Electron energy-loss spectrometry was employed to measure the white lines at
the L23 absorption edges of the 3d transition-metal oxides and lithium
transition-metal oxides. The white-line ratio (L3/L2) was found to increase
between d^0 and d^5 and decrease between d^5 and d^10, consistent with previous
results for the transition metals and their oxides. The intensities of the
white lines, normalized to the post-edge background, are linear for the 3d
transition-metal oxides and lithium transition-metal oxides. An empirical
correlation between normalized white-line intensity and 3d occupancy is
established. It provides a method for measuring changes in the 3d-state
occupancy. As an example, this empirical relationship is used to measure
changes in the transition-metal valences of Li_{1-x}Ni_{0.8}Co_{0.2}O_2 in the
range of 0 < x < 0.64. In these experiments the 3d occupancy of the nickel ion
decreased upon lithium deintercalation, while the cobalt valence remained
constant.Comment: 6 pages, 7 figure
Magnetic interactions in transition metal doped ZnO : An abinitio study
We calculate the nature of magnetic interactions in transition-metal doped
ZnO using the local spin density approximation and LSDA+\textit{U} method of
density functional theory. We investigate the following four cases: (i) single
transition metal ion types (Cr, Mn, Fe, Co, Ni and Cu) substituted at Zn sites,
(ii) substitutional magnetic transition metal ions combined with additional Cu
and Li dopants, (iii) substitutional magnetic transition metal ions combined
with oxygen vacancies and (iv) pairs of magnetic ion types (Co and Fe, Co and
Mn, etc.). Extensive convergence tests indicate that the calculated magnetic
ground state is unusually sensitive to the k-point mesh and energy cut-off, the
details of the geometry optimizations and the choice of the
exchange-correlation functional. We find that ferromagnetic coupling is
sometimes favorable for single type substitutional transition metal ions within
the local spin density approximation. However, the nature of magnetic
interactions changes when correlations on the transition-metal ion are treated
within the more realistic LSDA + \textit{U} method, often disfavoring the
ferromagnetic state. The magnetic configuration is sensitive to the detailed
arrangement of the ions and the amount of lattice relaxation, except in the
case of oxygen vacancies when an antiferromagnetic state is always favored.Comment: 11 pages, 17 figure
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Electroplating lithium transition metal oxides.
Materials synthesis often provides opportunities for innovation. We demonstrate a general low-temperature (260°C) molten salt electrodeposition approach to directly electroplate the important lithium-ion (Li-ion) battery cathode materials LiCoO2, LiMn2O4, and Al-doped LiCoO2. The crystallinities and electrochemical capacities of the electroplated oxides are comparable to those of the powders synthesized at much higher temperatures (700° to 1000°C). This new growth method significantly broadens the scope of battery form factors and functionalities, enabling a variety of highly desirable battery properties, including high energy, high power, and unprecedented electrode flexibility
Electronic structure of complex spd Hume-Rothery phases in transition-metal aluminides
The discovery of quasicrystals phases and approximants in Al(rich)-Mn system
has revived the interest for complex aluminides containing transition-metal
atoms. On one hand, it is now accepted that the Hume-Rothery stabilization
plays a crucial role. On the other hand, transition-metal atoms have also a
very important effect on their stability and their physical properties. In this
paper, we review studies that unifies the classical Hume-Rothery stabilization
for sp electron phases with the virtual bound state model for transition-metal
atoms embedded in the aluminum matrix. These studies lead to a new theory for
\"spd electron phases\". It is applied successfully to Al(Si)--transition-metal
alloys and it gives a coherent picture of their stability and physical
properties. These works are based on first-principles calculations of the
electronic structure and simplified models, compared to experimental results. A
more detailed review article is published in Prog. Mater. Sci. 50 (2005) p.
679-788
Threshold electronic structure at the oxygen K edge of 3d transition metal oxides: a configuration interaction approach
It has been generally accepted that the threshold structure observed in the
oxygen K edge X-ray absorption spectrum in 3d transition metal oxides
represents the electronic structure of the 3d transition metal. There is,
however, no consensus about the correct description. We present an
interpretation, which includes both ground state hybridization and electron
correlation. It is based on a configuration interaction cluster calculation
using a MO6 cluster. The oxygen K edge spectrum is calculated by annihilating a
ligand hole in the ground state and is compared to calculations representing
inverse photoemission experiments in which a 3d transition metal electron is
added. Clear differences are observed related to the amount of ligand hole
created in the ground state. Two "rules" connected to this are discussed.
Comparison with experimental data of some early transition metal compounds is
made and shows that this simple cluster approach explains the experimental
features quite well.Comment: 10 pages, submitted to Phys. Rev. B, tried to make a better PS file
Chemical control of orbital polarization in artificially structured transition-metal oxides: La2NiXO6 (X=B, Al, Ga, In) from first principles
The application of modern layer-by-layer growth techniques to
transition-metal oxide materials raises the possibility of creating new classes
of materials with rationally designed correlated electron properties. An
important step toward this goal is the demonstration that electronic structure
can be controlled by atomic composition. In compounds with partially occupied
transition-metal d shells, one important aspect of the electronic structure is
the relative occupancy of different d orbitals. Previous work has established
that strain and quantum confinement can be used to influence orbital occupancy.
In this paper we demonstrate a different modality for orbital control in
transition-metal oxide heterostructures, using density-functional band
calculations supplemented by a tight-binding analysis to show that the choice
of nontransition-metal counterion X in transition-metal oxide heterostructures
composed of alternating LaNiO3 and LaXO3 units strongly affects orbital
occupancy, changing the magnitude and in some cases the sign of the orbital
polarization
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