Connection between charge transfer and alloying core-level shifts based on density-functional calculations

The measurement of alloying core-level binding energy (CLBE) shifts has been used to give a precise meaning to the fundamental concept of charge transfer. Here, ab-initio density-functional calculations for the intermetallic compound MgAu are used to investigate models which try to make a connection between the core levels shifts and charge transfer. The calculated CLBE shifts agree well with experiment, and permit an unambiguous separation into initial-state and screening contributions. Interestingly, the screening contribution is large and cannot be neglected in any reasonable description. Comparison of the calculated results with the predictions of simple models show that these models are not adequate to describe the realistic situation. On the positive side, the accuracy of the density-functional calculations indicates that the combination of experiments with such calculations is a powerful tool to investigate unknown systems.Comment: RevTeX 10 pages incl 8 figure

Reconstruction Mechanism of FCC Transition-Metal (001) Surfaces

The reconstruction mechanism of (001) fcc transition metal surfaces is investigated using a full-potential all-electron electronic structure method within density-functional theory. Total-energy supercell calculations confirm the experimental finding that a close-packed quasi-hexagonal overlayer reconstruction is possible for the late 5$d$-metals Ir, Pt, and Au, while it is disfavoured in the isovalent 4$d$ metals (Rh, Pd, Ag). The reconstructive behaviour is driven by the tensile surface stress of the unreconstructed surfaces; the stress is significantly larger in the 5$d$ metals than in 4$d$ ones, and only in the former case it overcomes the substrate resistance to the required geometric rearrangement. It is shown that the surface stress for these systems is due to $d$ charge depletion from the surface layer, and that the cause of the 4th-to-5th row stress difference is the importance of relativistic effects in the 5$d$ series.Comment: RevTeX 3.0, 12 pages, 1 PostScript figure available upon request] 23 May 199

Ab-initio procedure for effective models of correlated materials with entangled band structure

We present a first-principles method for deriving effective low-energy models of electrons in solids having entangled band structure. The procedure starts with dividing the Hilbert space into two subspaces, the low-energy part ("$d$ space'') and the rest of the space ("$r$ space''). The low-energy model is constructed for the $d$ space by eliminating the degrees of freedom of the $r$ space. The thus derived model contains the strength of electron correlation expressed by a partially screened Coulomb interaction, calculated in the constrained random-phase-approximation (cRPA) where screening channels within the $d$ space, $P_d$, are subtracted. One conceptual problem of this established downfolding method is that for entangled bands it is not clear how to cut out the $d$ space and how to distinguish $P_d$ from the total polarization. Here, we propose a simple procedure to overcome this difficulty. In our scheme, the $d$ subspace is cut out from the Hilbert space of the Kohn Sham eigenfunctions with the help of a procedure to construct a localized Wannier basis. The $r$ subspace is constructed as the complementary space orthogonal to the $d$ subspace. After this disentanglement, $P_d$ becomes well defined. Using the disentangled bands, the effective parameters are uniquely determined in the cRPA. The method is successfully applied to 3$d$ transition metals.Comment: 14 pages, 4 figure

GW correlation effects on plutonium quasiparticle energies: changes in crystal-field splitting

We present results for the electronic structure of plutonium by using a recently developed quasiparticle self-consistent $GW$ method (\qsgw). We consider a paramagnetic solution without spin-orbit interaction as a function of volume for the face-centered cubic (fcc) unit cell. We span unit-cell volumes ranging from 10% greater than the equilibrium volume of the $\delta$ phase to 90 % of the equivalent for the $\alpha$ phase of Pu. The self-consistent $GW$ quasiparticle energies are compared to those obtained within the Local Density Approximation (LDA). The goal of the calculations is to understand systematic trends in the effects of electronic correlations on the quasiparticle energy bands of Pu as a function of the localization of the $f$ orbitals. We show that correlation effects narrow the $f$ bands in two significantly different ways. Besides the expected narrowing of individual $f$ bands (flatter dispersion), we find that an even more significant effect on the $f$ bands is a decrease in the crystal-field splitting of the different bands.Comment: 9 pages, 7 figures, 3 table

Electronic and structural properties of GaN by the full-potential LMTO method : the role of the dd electrons

The structural and electronic properties of cubic GaN are studied within the local density approximation by the full-potential linear muffin-tin orbitals method. The Ga $3d$ electrons are treated as band states, and no shape approximation is made to the potential and charge density. The influence of $d$ electrons on the band structure, charge density, and bonding properties is analyzed. It is found that due to the energy resonance of the Ga 3$d$ states with nitrogen 2$s$ states, the cation $d$ bands are not inert, and features unusual for a III-V compound are found in the lower part of the valence band and in the valence charge density and density of states. To clarify the influence of the Ga $d$ states on the cohesive properties, additional full and frozen--overlapped-core calculations were performed for GaN, cubic ZnS, GaAs, and Si. The results show, in addition to the known importance of non-linear core-valence exchange-correlation corrections, that an explicit description of closed-shell repulsion effects is necessary to obtain accurate results for GaN and similar systems. In summary, GaN appears to be somewhat exceptional among the III-V compounds and reminiscent of II-VI materials, in that its band structure and cohesive properties are sensitive to a proper treatment of the cation $d$ bands, as a result of the presence of the latter in the valence band range.Comment: ( 20 REVTEX-preprint pages (REVTEX macros are included) 8 figures available upon reques

Screened Coulomb interaction in the maximally localized Wannier basis

We discuss a maximally localized Wannier function approach for constructing lattice models from first-principles electronic structure calculations, where the effective Coulomb interactions are calculated in the constrained random-phase-approximation. The method is applied to the 3d transition metals and a perovskite (SrVO_3). We also optimize the Wannier functions by unitary transformation so that U is maximized. Such Wannier functions unexpectedly turned out to be very close to the maximally localized ones.Comment: 22 pages, 6 figure

Quasiparticles in the Kondo lattice model at partial fillings of the conduction band

We study the spectral properties of the one-dimensional Kondo lattice model as function of the exchange coupling, the band filling, and the quasimomentum in the ferromagnetic and paramagnetic phase. Using the density-matrix renormalization group method, we compute the dispersion relation of the quasiparticles, their lifetimes, and the Z-factor. As a main result, we provide evidence for the existence of the spinpolaron at partial band fillings. We find that the quasiparticle lifetime differs by orders of magnitude between the ferromagnetic and paramagnetic phase and depends strongly on the quasimomentum.Comment: 9 pages, 9 figure

Extracting convergent surface energies from slab calculations

The formation energy of a solid surface can be extracted from slab calculations if the bulk energy per atom is known. It has been pointed out previously that the resulting surface energy will diverge with slab thickness if the bulk energy is in error, in the context of calculations which used different methods to study the bulk and slab systems. We show here that this result is equally relevant for state-of-the-art computational methods which carefully treat bulk and slab systems in the same way. Here we compare different approaches, and present a solution to the problem that eliminates the divergence and leads to rapidly convergent and accurate surface energies.Comment: 3 revtex pages, 1 figure, in print on J. Phys. Cond. Mat

Realistic many-body models for Manganese Monoxide under pressure

In materials like transition metals oxides where electronic Coulomb correlations impede a description in terms of standard band-theories, the application of genuine many-body techniques is inevitable. Interfacing the realism of density-functional based methods with the virtues of Hubbard-like Hamiltonians, requires the joint ab initio construction of transfer integrals and interaction matrix elements (like the Hubbard U) in a localized basis set. In this work, we employ the scheme of maximally localized Wannier functions and the constrained random phase approximation to create effective low-energy models for Manganese monoxide, and track their evolution under external pressure. We find that in the low pressure antiferromagnetic phase, the compression results in an increase of the bare Coulomb interaction for specific orbitals. As we rationalized in recent model considerations [Phys. Rev. B 79, 235133 (2009)], this seemingly counter-intuitive behavior is a consequence of the delocalization of the respective Wannier functions. The change of screening processes does not alter this tendency, and thus, the screened on-site component of the interaction - the Hubbard U of the effective low-energy system - increases with pressure as well. The orbital anisotropy of the effects originates from the orientation of the orbitals vis-a-vis the deformation of the unit-cell. Within the high pressure paramagnetic phase, on the other hand, we find the significant increase of the Hubbard U is insensitive to the orbital orientation and almost exclusively owing to a substantial weakening of screening channels upon compression.Comment: 13 pages, 6 figure