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Computing phonons from first-principles is typically considered a solved problem, yet inadequacies in existing techniques continue to yield deficient results in systems with sensitive phonons. Here we circumvent this issue using the lone irreducible derivative (LID) and bundled irreducible derivative (BID) approaches to computing phonons via finite displacements, where the former optimizes precision via energy derivatives and the latter provides the most efficient algorithm using force derivatives. A condition number optimized (CNO) basis for BID is derived which guarantees the minimum amplification of error. Additionally, a hybrid LID-BID approach is formulated, where select irreducible derivatives computed using LID replace BID results. We illustrate our approach on two prototypical systems with sensitive phonons: the shape memory alloy AuZn and metallic lithium. Comparing our resulting phonons in the aforementioned crystals to calculations in the literature reveals nontrivial inaccuracies. Our approaches can be fully automated, making them well suited for both niche systems of interest and high throughput approaches.

Actinide-based compounds exhibit unique physics due to the presence of 5f electrons, and serve in many cases as important technological materials. Targeted thin film synthesis of actinide materials has been successful in generating high-purity specimens in which to study individual physical phenomena. These films have enabled the study of the unique electron configuration, strong mass renormalization, and nuclear decay in actinide metals and compounds. The growth of these films, as well as their thermophysical, magnetic, and topological properties, have been studied in a range of chemistries, albeit far fewer than most classes of thin film systems. This relative scarcity is the result of limited source material availability and safety constraints associated with the handling of radioactive materials. Here, we review recent work on the synthesis and characterization of actinide-based thin films in detail, describing both synthesis methods and modelling techniques for these materials. We review reports on pyrometallurgical, solution-based, and vapor deposition methods. We highlight the current state-of-the-art in order to construct a path forward to higher quality actinide thin films and heterostructure devices., Comment: 23 pages, 5 figures

Two dimensional (2D) transition-metal dichalcogenide (TMD) based semiconductors have generated intense recent interest due to their novel optical and electronic properties, and potential for applications. In this work, we characterize the atomic and electronic nature of intrinsic point defects found in single crystals of these materials synthesized by two different methods - chemical vapor transport and self-flux growth. Using a combination of scanning tunneling microscopy (STM) and scanning transmission electron microscopy (STEM), we show that the two major intrinsic defects in these materials are metal vacancies and chalcogen antisites. We show that by control of the synthetic conditions, we can reduce the defect concentration from above $10^{13} /cm^2$ to below $10^{11} /cm^2$. Because these point defects act as centers for non-radiative recombination of excitons, this improvement in material quality leads to a hundred-fold increase in the radiative recombination efficiency.

MoTe_2, with the orthorhombic T_d phase, is a new type (type-II) of Weyl semimetal, where the Weyl Fermions emerge at the boundary between electron and hole pockets. Non-saturating magnetoresistance (MR), and superconductivity were also observed in T_d-MoTe_2. Understanding the superconductivity in T_d-MoTe_2, which was proposed to be topologically non-trivial, is of eminent interest. Here, we report high-pressure (p_max = 1.3 GPa) muon spin rotation experiments on the temperature-dependent magnetic penetration depth in T_d-MoTe_2. A substantial increase of the superfluid density n_s/m^* and a linear scaling with T_c is observed under pressure. Moreover, the superconducting order parameter in T_d-MoTe_2 is determined to be two gap (s+s)-wave symmetric. We also excluded time reversal symmetry breaking in the SC state with sensitive zero-field ${\mu}$SR experiments. Considering the previous report \cite{Balicas1} on the strong suppression of T_c in T_d-MoTe_2 by disorder, we suggest that s^{+-} (topological order parameter) state is more likely to be realized in MoTe_2 than the s^{++} (trivial) state. Should s^{+-} be the SC gap symmetry, the T_d-MoTe_2 is, to our knowledge, the first known example of a time reversal invariant topological (Weyl) superconductor., Comment: 15 pages and 9 figures

Here we introduce a new approach to compute the finite temperature lattice dynamics from first-principles via the newly developed slave mode expansion. We study PbTe where inelastic neutron scattering (INS) reveals strong signatures of nonlinearity as evidenced by anomalous features which emerge in the phonon spectra at finite temperature. Using our slave mode expansion in the classical limit, we compute the vibrational spectra and show remarkable agreement with temperature dependent INS measurements. Furthermore, we resolve experimental controversy by showing that there are no appreciable local nor global spontaneously broken symmetries at finite temperature and that the anomalous spectral features simply arise from two anharmonic interactions. Our approach should be broadly applicable across the periodic table.

Dynamical mean field theory calculations are used to show that for late transition-metal-oxides a critical variable for the Mott/charge-transfer transition is the number of d-electrons, which is determined by charge transfer from oxygen ions. Insulating behavior is found only for a narrow range of d-occupancy, irrespective of the size of the intra-d Coulomb repulsion. The result is useful in interpreting 'density functional +U' and 'density functional plus dynamical mean field' methods in which additional correlations are applied to a specific set of orbitals and an important role is played by the 'double counting correction' which dictates the occupancy of these correlated orbitals. General considerations are presented and are illustrated by calculations for two representative transition metal oxide systems: layered perovskite Cu-based "high-Tc" materials, an orbitally non-degenerate electronically quasi-two dimensional systems, and pseudocubic rare earch nickelates, an orbitally degenerate electronically three dimensional system. Density functional calculations yield d-occupancies very far from the Mott metal-insulator phase boundary in the nickelate materials, but closer to it in the cuprates, indicating the sensitivity of theoretical models of the cuprates to the choice of double counting correction and corroborating the critical role of lattice distortions in attaining the experimentally observed insulating phase in the nickelates., Comment: 10+ pages, 5 figures

Dynamical mean field methods are used to calculate the phase diagram, many-body density of states, relative orbital occupancy and Fermi surface shape for a realistic model of $LaNiO_3$-based superlattices. The model is derived from density functional band calculations and includes oxygen orbitals. The combination of the on-site Hunds interaction and charge-transfer between the transition metal and the oxygen orbitals is found to reduce the orbital polarization far below the levels predicted either by band structure calculations or by many-body analyses of Hubbard-type models which do not explicitly include the oxygen orbitals. The findings indicate that heterostructuring is unlikely to produce one band model physics and demonstrate the fundamental inadequacy of modeling the physics of late transition metal oxides with Hubbard-like models., Comment: Values of orbitals polarizations reported in Fig. 2 corrected. We thank E. Benckiser and M. Wu for pointing out the errors

The dynamical mean-field concept of approximating an unsolvable many-body problem in terms of the solution of an auxiliary quantum impurity problem, introduced to study bulk materials with a continuous energy spectrum, is here extended to molecules, i.e., finite systems with a discrete energy spectrum. The application to small clusters of hydrogen atoms yields ground state energies which are competitive with leading quantum chemical approaches at intermediate and large interatomic distances as well as good approximations to the excitation spectrum., Comment: 5 pages, 4 figures

A combination of Density Functional Theory and the Dynamical Mean Field theory (DMFT) is used to calculate the magnetic susceptibility, heat capacity, and the temperature dependence of the valence band photoemission spectra. The continuous-time hybridization expansion quantum Monte-Carlo is utilized to provide the first approximation-free DMFT solution of \emph{fcc} $\delta$-Pu which includes the full rotationally-invariant exchange interaction. We predict that $\delta$-Pu has a Pauli-like magnetic susceptibility near ambient temperature, as in experiment, indicating that electronic coherence causes the absence of local moments. Additionally, We show that volume expansion causes a crossover from incoherent to coherent electronic behavior at increasingly lower temperatures.

We revisit Nagaoka ferromagnetism in the U=oo Hubbard model within the dynamical mean-field theory (DMFT) using the recently developed continuous time quantum Monte Carlo method as the impurity solver. The stability of Nagaoka ferromagnetism is studied as a function of the temperature, the doping level, and the next-nearest-neighbor lattice hopping t'. We found that the nature of the phase transition as well as the stability of the ferromagnetic state is very sensitive to the t' hopping. Negative t'=-0.1t stabilizes ferromagnetism up to higher doping levels. The paramagnetic state is reached through a first order phase transition. Alternatively, a second order phase transition is observed at t'=0. Very near half-filling, the coherence temperature T_{coh} of the paramagnetic metal becomes very low and ferromagnetism evolves out of an incoherent metal rather than conventional Fermi liquid. We use the DMFT results to benchmark slave-boson method which might be useful in more complicated geometries., Comment: 10 pages, 11 figures

We present a detailed analysis of the one-electron physics of the actinides. Various LMTO basis sets are analyzed in order to determine a robust bare Hamiltonian for the actinides. The hybridization between f- an spd- states is compared with the f-f hopping in order to understand the Anderson-like and Hubbard-like contributions to itineracy in the actinides. We show that both contributions decrease strongly as one move from the light actinides to the heavy actinides, while the Anderson-like contribution dominates in all cases. A real-space analysis of the band structure shows that nearest-neighbor hopping dominates the physics in these materials. Finally, we discuss the implications of our results to the delocalization transition as function of atomic number across the actinide series., Comment: 11 pages, 7 figures

The cobaltates have demonstrated a wide variety complex behavior. The Na rich region of the phase diagram displays various degrees of anomalous behavior, such as Curie-Weiss behavior near a band insulator\cite{Foo:2004}, charge disproportionation\cite{Mukhamedshin:2005}, and non-Fermi-liquid behavior in the resistivity\cite{Foo:2004}. Alternatively, the Na poor region of the phase diagram appears to be a Fermi-liquid. The magnetic susceptibility displays Pauli behavior, the resistivity is roughly quadratic at low temperatures\cite{Foo:2004}, and the system appears to be homogeneous\cite{Mukhamedshin:2005}. Therefore, the Na poor region of the phase diagram seems like a natural starting point to attempt to explain the ARPES experiments and heat capacity measurements from a quantitative standpoint.

Increasing experimental evidence is building which indicates that signatures of strong correlations are present in the Na rich region of Na$_x$CoO$_2$ (ie. $x\approx0.7$) and absent in the Na poor region (ie. $x\approx0.3$). This is unexpected given that NaCoO$_2$ is a band insulator and CoO$_2$ has an integer filled open shell making it a candidate for strong correlations. We explain these experimental observations by presenting a minimal low-energy Hamiltonian for the cobaltates and solving it within LDA+DMFT. The Na potential is shown to be a key element in understanding correlations in this material. Furthermore, LDA calculations for the realistic Na ordering predict a \emph{binary} perturbation of the Co sites which correlates with the Na$_1$ sites (ie. Na sites above/below Co sites).

We present a review of the basic ideas and techniques of the spectral density functional theory which are currently used in electronic structure calculations of strongly-correlated materials where the one-electron description breaks down. We illustrate the method with several examples where interactions play a dominant role: systems near metal-insulator transition, systems near volume collapse transition, and systems with local moments., Comment: 88 pages. Submitted to Review of Modern Physics

We report on a significant failure of LDA and GGA to reproduce the phase stability and thermodynamics of mixed-valence Li$_x$FePO$_4$ compounds. Experimentally, Li$_x$FePO$_4$ compositions ($0 \leq x \leq 1$) are known to be unstable and phase separate into Li FePO$_4$ and FePO$_4$. However, first-principles calculations with LDA/GGA yield energetically favorable intermediate compounds an d hence no phase separation. This qualitative failure of LDA/GGA seems to have its origin in the LDA/GGA self-interaction which de localizes charge over the mixed-valence Fe ions, and is corrected by explicitly considering correlation effects in this material. This is demonstrated with LDA+U calculations which correctly predict phase separation in Li$_x$FePO$_4$ for $U-J \gtrsim 3.5$eV. T he origin of the destabilization of intermediate compounds is identified as electron localization and charge ordering at different iron sites. Introduction of correlation also yields more accurate electrochemical reaction energies between FePO$_4$/Li$_x$FePO$_ 4$ and Li/Li$^+$ electrodes., Comment: 12 pages, 5 figures, Phys. Rev. B 201101R, 2004

Density functional theory (DFT) within the local density approximation (LDA) is used to understand the electronic properties of Na1/3CoO2 and Na1/3CoO2(H2O)4/3, which was recently found to be superconducting1. Comparing the LDA charge density of CoO2 and the Na doped phases indicates that doping does not simply add electrons to the t2g states. In fact, the electron added in the t2g state is dressed by hole density in the eg state and electron density in the oxygen states via rehybridization. In order to fully understand this phenomenon, a simple extension of the Hubbard Hamiltonian is proposed and solved using the dynamical mean-field theory (DMFT). This simple model confirms that the rehybridization is driven by a competition between the on-site coulomb interaction and the hybridization. In addition, we find that the presence of eg-oxygen hybridization effectively screens the low energy excitations. To address the role that water plays in creating the superconducting state, we compare the LDA band structure of Na1/3CoO2 and its hydrated counterpart. This demonstrates that hydration does cause the electronic structure to become more two-dimensional., Comment: 12 pages, 4 figures