60 research outputs found
First principles study of electronic and structural properties of CuO
We investigate the electronic and structural properties of CuO, which shows
significant deviations from the trends obeyed by other transition-metal
monoxides. Using an extended Hubbard corrective functional, we uncover an
orbitally ordered insulating ground state for the cubic phase of this material,
which was expected but never found before. This insulating state results from a
fine balance between the tendency of Cu to complete its d-shell and Hund's rule
magnetism. Starting from the ground state for the cubic phase, we also study
tetragonal distortions of the unit cell (recently reported in experiments), the
consequent electronic reorganizations and identify the equilibrium structure.
Our calculations reveal an unexpected richness of possible magnetic and orbital
orders, relatively close in energy to the ground state, whose stability depends
on the sign and entity of distortion.Comment: 9 pages, 9 figure
Structure and energetics of solvated ferrous and ferric ions: Car-Parrinello molecular dynamics in the DFT+U formalism
We implemented a rotationally-invariant Hubbard U extension to
density-functional theory in the Car-Parrinello molecular dynamics framework,
with the goal of bringing the accuracy of the DFT+U approach to
finite-temperature simulations, especially for liquids or solids containing
transition-metal ions. First, we studied the effects on the Hubbard U on the
static equilibrium structure of the hexa-aqua ferrous and ferric ions, and the
inner-sphere reorganization energy for the electron-transfer reaction between
aqueous ferrous and ferric ions. It is found that the reorganization energy is
increased, mostly as a result of the Fe-O distance elongation in the hexa-aqua
ferrous ion. Second, we performed a first-principles molecular dynamics study
of the solvation structure of the two aqueous ferrous and ferric ions. The
Hubbard term is found to change the Fe-O radial distribution function for the
ferrous ion, while having a negligible effect on the aqueous ferric ion.
Moreover, the frequencies of vibrations between Fe and oxygen atoms in the
first-solvation shell are shown to be unaffected by the Hubbard corrections for
both ferrous and ferric ions.Comment: 13 pages, 2 figures, 1 table. Submitted to Journal of
Electroanalytical Chemistr
Simulation of Heme using DFT+U: a step toward accurate spin-state energetics
We investigate the DFT+U approach as a viable solution to describe the
low-lying states of ligated and unligated iron heme complexes. Besides their
central role in organometallic chemistry, these compounds represent a
paradigmatic case where LDA, GGA, and common hybrid functionals fail to
reproduce the experimental magnetic splittings. In particular, the imidazole
pentacoordinated heme is incorrectly described as a triplet by all usual DFT
flavors. In this study we show that a U parameter close to 4 eV leads to spin
transitions and molecular geometries in quantitative agreement with
experiments, and that DFT+U represents an appealing tool in the description of
iron porphyrin complexes, at a much reduced cost compared to correlated
quantum-chemistry methods. The possibility of obtaining the U parameter from
first-principles is explored through a self-consistent linear-response
formulation. We find that this approach, which proved to be successful in other
iron systems, produces in this case some overestimation with respect to the
optimal values of U.Comment: To be published in The Journal of Physical Chemistry B 30 pages, 15
figure
Energetics and cathode voltages of LiMPO olivines (M = Fe, Mn) from extended Hubbard functionals
Transition-metal compounds pose serious challenges to first-principles
calculations based on density-functional theory (DFT), due to the inability of
most approximate exchange-correlation functionals to capture the localization
of valence electrons on their states, essential for a predictive modeling
of their properties. In this work we focus on two representatives of a well
known family of cathode materials for Li-ion batteries, namely the orthorhombic
LiMPO olivines (M = Fe, Mn). We show that extended Hubbard functionals with
on-site () and inter-site () interactions (so called DFT+U+V) can predict
the electronic structure of the mixed-valence phases, the formation energy of
the materials with intermediate Li contents, and the overall average voltage of
the battery with remarkable accuracy. We find, in particular, that the
inclusion of inter-site interactions in the corrective Hamiltonian improves
considerably the prediction of thermodynamic quantities when electronic
localization occurs in the presence of significant interatomic hybridization
(as is the case for the Mn compound), and that the self-consistent evaluation
of the effective interaction parameters as material- and ground-state-dependent
quantities allows the prediction of energy differences between different phases
and concentrations
Electronic-enthalpy functional for finite systems under pressure
We introduce the notion of electronic enthalpy for first-principles
structural and dynamical calculations of finite systems under pressure. An
external pressure field is allowed to act directly on the electronic structure
of the system studied via the ground-state minimization of the functional
, where is the quantum volume enclosed by a charge
isosurface. The Hellmann-Feynman theorem applies, and assures that the ionic
equations of motion follow an isoenthalpic dynamics. No pressurizing medium is
explicitly required, while coatings of environmental ions or ligands can be
introduced if chemically relevant. We apply this novel approach to the study of
group-IV nanoparticles during a shock wave, highlighting the significant
differences inthe plastic or elastic response of the diamond cage under load,
and their potential use as novel nanostructured impact-absorbing materials.Comment: 4 pages, 4 figure
Spin-state crossover and hyperfine interactions of ferric iron in MgSiO perovskite
Using density functional theory plus Hubbard calculations, we show that
the ground state of (Mg,Fe)(Si,Fe)O perovskite, a major mineral phase in
the Earth's lower mantle, has high-spin ferric iron () at both the
dodecahedral (A) and octahedral (B) site. As the pressure increases, the B-site
iron undergoes a spin-state crossover to the low-spin state (), while
the A-site iron remains in the high-spin state. Our calculation shows that the
B-site spin-state crossover in the pressure range of 40-70 GPa is accompanied
by a noticeable volume reduction and an increase in quadrupole splitting,
consistent with recent X-ray diffraction and M\"ossbauer spectroscopy
measurements. The volume reduction leads to a significant softening in the bulk
modulus, which suggests a possible source of seismic velocity anomalies in the
lower mantle.Comment: 11 pages, 4 figures, 1 tabl
Hubbard parameters from density-functional perturbation theory
We present a transparent and computationally efficient approach for the
first-principles calculation of Hubbard parameters from linear-response theory.
This approach is based on density-functional perturbation theory and the use of
monochromatic perturbations. In addition to delivering much improved
efficiency, the present approach makes it straightforward to calculate
automatically these Hubbard parameters for any given system, with tight
numerical control on convergence and precision. The effectiveness of the method
is showcased in three case studies - CuO, NiO, and LiCoO - and by the
direct comparison with finite differences in supercell calculations.Comment: 17 pages, 6 figure
Self-consistent Hubbard parameters from density-functional perturbation theory in the ultrasoft and projector-augmented wave formulations
The self-consistent evaluation of Hubbard parameters using linear-response
theory is crucial for quantitatively predictive calculations based on
Hubbard-corrected density-functional theory. Here, we extend a
recently-introduced approach based on density-functional perturbation theory
(DFPT) for the calculation of the on-site Hubbard to also compute the
inter-site Hubbard . DFPT allows to reduce significantly computational
costs, improve numerical accuracy, and fully automate the calculation of the
Hubbard parameters by recasting the linear response of a localized perturbation
into an array of monochromatic perturbations that can be calculated in the
primitive cell. In addition, here we generalize the entire formalism from
norm-conserving to ultrasoft and projector-augmented wave formulations, and to
metallic ground states. After benchmarking DFPT against the conventional
real-space Hubbard linear response in a supercell, we demonstrate the
effectiveness of the present extended Hubbard formulation in determining the
equilibrium crystal structure of LiMnPO (x=0,1) and the subtle
energetics of Li intercalation.Comment: 15 pages, 3 figure
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