Garnet-type Li7La3Zr2O12 (LLZO) is a solid electrolyte material with a low-conductivity tetragonal and a high-conductivity cubic phase. Using density-functional theory and variable cell shape molecular dynamics simulations, we show that the tetragona
l phase stability is dependent on a simultaneous ordering of the Li ions on the Li sublattice and a volume-preserving tetragonal distortion that relieves internal structural strain. Supervalent doping introduces vacancies into the Li sublattice, increasing the overall entropy and reducing the free energy gain from ordering, eventually stabilizing the cubic phase. We show that the critical temperature for cubic phase stability is lowered as Li vacancy concentration (dopant level) is raised and that an activated hop of Li ions from one crystallographic site to another always accompanies the transition. By identifying the relevant mechanism and critical concentrations for achieving the high conductivity phase, this work shows how targeted synthesis could be used to improve electrolytic performance.
By combining first principles calculations and experimental XPS measurements, we investigate the electronic structure of potential Li-ion battery cathode materials LiMPO4 (M=Mn,Fe,Co,Ni) to uncover the underlying mechanisms that determine small hole
polaron formation and migration. We show that small hole polaron formation depends on features in the electronic structure near the valence-band maximum and that, calculationally, these features depend on the methodology chosen for dealing with the correlated nature of the transition-metal d-derived states in these systems. Comparison with experiment reveals that a hybrid functional approach is superior to GGA+U in correctly reproducing the XPS spectra. Using this approach we find that LiNiPO4 cannot support small hole polarons, but that the other three compounds can. The migration barrier is determined mainly by the strong or weak bonding nature of the states at the top of the valence band, resulting in a substantially higher barrier for LiMnPO4 than for LiCoPO4 or LiFePO4.
We report first-principles density-functional theory studies of native point defects and defect complexes in olivine-type LiFePO4, a promising candidate for rechargeable Li-ion battery electrodes. The defects are characterized by their formation ener
gies which are calculated within the GGA+U framework. We find that native point defects are charged, and each defect is stable in one charge state only. Removing electrons from the stable defects always generates defect complexes containing small hole polarons. Defect formation energies, hence concentrations, and defect energy landscapes are all sensitive to the choice of atomic chemical potentials which represent experimental conditions. One can, therefore, suppress or enhance certain native defects in LiFePO4 via tuning the synthesis conditions. Based on our results, we provide insights on how to obtain samples in experiments with tailored defect concentrations for targeted applications. We also discuss the mechanisms for ionic and electronic conduction in LiFePO4 and suggest strategies for enhancing the electrical conductivity.
Using first principles calculations, we analyze structural and magnetic trends as a function of charge doping and pressure in BaFe$_2$As$_2$, and compare to experimentally established facts. We find that density functional theory, while accurately re
producing the structural and magnetic ordering at ambient pressure, fails to reproduce some structural trends as pressure is increased. Most notably, the Fe-As bondlength which is a gauge of the magnitude of the magnetic moment, $mu$, is rigid in experiment, but soft in calculation, indicating residual local Coulomb interactions. By calculating the magnitude of the magnetic ordering energy, we show that the disruption of magnetic order as a function of pressure or doping can be qualitatively reproduced, but that in calculation, it is achieved through diminishment of $|mu|$, and therefore likely does not reflect the same physics as detected in experiment. We also find that the strength of the stripe order as a function of doping is strongly site-dependent: magnetism decreases monotonically with the number of electrons doped at the Fe site, but increases monotonically with the number of electrons doped at the Ba site. Intra-planar magnetic ordering energy (the difference between checkerboard and stripe orderings) and interplanar coupling both follow a similar trend. We also investigate the evolution of the orthorhombic distortion, $e=(a-b)/(a+b),$ as a function of $mu$, and find that in the regime where experiment finds a linear relationship, our calculations are impossible to converge, indicating that in density functional theory, the transition is first order, signalling anomalously large higher order terms in the Landau functional.
One year after their initial discovery, two schools of thought have crystallized regarding the electronic structure and magnetic properties of ferropnictide systems. One postulates that these are itinerant weakly correlated metallic systems that beco
me magnetic by virtue of spin-Peierls type transition due to near-nesting between the hole and the electron Fermi surface pockets. The other argues these materials are strongly or at least moderately correlated, the electrons are considerably localized and close to a Mott-Hubbard transition, with the local magnetic moments interacting via short-range superexchange. In this paper we argue that neither picture is fully correct. The systems are moderately correlated, but with correlations driven by Hunds rule coupling rather than by the on-site Hubbard repulsion. The iron moments are largely local, driven by Hunds intra-atomic exchange. Superexchange is not operative and the interactions between the Fe moments are considerably long-range and driven mostly by one-electron energies of all occupied states.
We argue that the newly discovered superconductivity in a nearly magnetic, Fe-based layered compound is unconventional and mediated by antiferromagnetic spin fluctuations, though different from the usual superexchange and specific to this compound. T
his resulting state is an example of extended s-wave pairing with a sign reversal of the order parameter between different Fermi surface sheets. The main role of doping in this scenario is to lower the density of states and suppress the pair-breaking ferromagnetic fluctuations.
The 2008 discovery of superconducting ferropnictides with Tc~26K-56K introduced a new family of materials into the category of high Tc superconductors. The ongoing project of understanding the superconducting mechanism and pairing symmetry has alread
y revealed a complicated and often contradictory underlying picture of the structural and magnetic properties. There is an almost unprecedented sensitivity of the calculated magnetism and Fermi surface to structural details that prohibits correspondence with experiment. Furthermore, experimental probes of the order parameter symmetry are in surprisingly strong disagreement, even considering the relative immaturity of the field. Here we outline all of the various and seemingly contradictory evidences, both theoretical and experimental, and show that they can be rectified if the system is assumed to be highly magnetic with a spin density wave that is well-defined but with magnetic twin and anti-phase boundaries that are dynamic on the time-scale of experiments. Under this assumption, we find that our calculations can accurately reproduce even very fine details of the structure, and a natural explanation for the temperature separation of structural and magnetic transitions is provided. Thus, our theory restores agreement between experiment and theory in crucial areas, making further cooperative progress possible on both fronts. We believe that fluctuating magnetic domains will be an essential component of unravelling the interplay between magnetic interactions and superconductivity in these newest high Tc superconductors.
First principles calculations of magnetic and, to a lesser extent, electronic properties of the novel LaFeAsO-based superconductors show substantial apparent controversy, as opposed to most weakly or strongly correlated materials. Not only do differe
nt reports disagree about quantitative values, there is also a schism in terms of interpreting the basic physics of the magnetic interactions in this system. In this paper, we present a systematic analysis using four different first principles methods and show that while there is an unusual sensitivity to computational details, well-converged full-potential all-electron results are fully consistent among themselves. What makes results so sensitive and the system so different from simple local magnetic moments interacting via basic superexchange mechanisms is the itinerant character of the calculated magnetic ground state, where very soft magnetic moments and long-range interactions are characterized by a particular structure in the reciprocal (as opposed to real) space. Therefore, unravelling the magnetic interactions in their full richness remains a challenging, but utterly important task.
The concept of a CDW induced by Fermi-surface nesting originated from the Peierls idea of electronic instabilities in purely 1D metals and is now often applied to charge ordering in real low-dimensional materials. The idea is that if Fermi surface co
ntours coincide when shifted along the observed CDW wave vector, then the CDW is considered to be nesting-derived. We show that in most cases this procedure has no predictive power, since Fermi surfaces either do not nest at the right wave vector, or nest more strongly at the wrong vector. We argue that only a tiny fraction, if any, of the observed charge ordering phase transitions are true analogues of the Peierls instability because electronic instabilities are easily destroyed by even small deviations from perfect nesting conditions. Using prototypical CDW materials NbSe$_2$, TaSe$_2$, and CeTe$_3$, we show that such conditions are hardly ever fulfilled, and that the CDW phases are actually structural phase transitions, driven by the concerted action of electronic and ionic subsystems, textit{i.e.,} textbf{q}-dependent electron-phonon coupling plays an indispensable part. We also show mathematically that the original Peierls construction is so fragile as to be unlikely to apply to real materials. We argue that no meaningful distinction between a CDW and an incommensurate lattice transition exists.
