Unconventional superconductivity without doping in infinite-layer nickelates under pressure.

High-temperature unconventional superconductivity quite generically emerges from doping a strongly correlated parent compound, often (close to) an antiferromagnetic insulator. The recently developed dynamical vertex approximation is a state-of-the-art technique that has quantitatively predicted the superconducting dome of nickelates. Here, we apply it to study the effect of pressure in the infinite-layer nickelate SrxPr1-xNiO2. We reproduce the increase of the critical temperature (Tc) under pressure found in experiment up to 12 GPa. According to our results, Tc can be further increased with higher pressures. Even without Sr-doping the parent compound, PrNiO2, will become a high-temperature superconductor thanks to a strongly enhanced self-doping of the Ni d x 2 - y 2 orbital under pressure. With a maximal Tc of 100 K around 100 GPa, nickelate superconductors can reach that of the best cuprates.

Resistance saturation in semi-conducting polyacetylene molecular wires.

Realizing the promises of molecular electronic devices requires an understanding of transport on the nanoscale. Here, we consider a Su-Schrieffer-Heeger model for semi-conducting trans-polyacetylene molecular wires in which we endow charge carriers with a finite lifetime. The aim of this exercise is two-fold: (i) the simplicity of the model allows an insightful numerical and analytical comparison of the Landauer and Kubo linear-response formalism; (ii) we distill the prototypical characteristics of charge transport through gapped mesoscopic systems and compare these to bulk semiconductors. We find that both techniques yield a residual differential conductance at low temperatures for contacted polyacetylene chains of arbitrary length-in line with the resistivity saturation in some correlated narrow-gap semiconductors. Quantitative agreement, however, is limited to not too long molecules. Indeed, while the Landauer transmission is suppressed exponentially with the system size, the Kubo response only decays hyperbolically. Our findings inform the choice of transport methodologies for the ab initio modelling of molecular devices.

Pb10-xCux(PO4)6O: a Mott or charge transfer insulator in need of further doping for (super)conductivity.

We briefly review the status quo of research on the putative superconductor Pb9Cu(PO4)6O also known as LK-99. Further, we provideab initioderived tight-binding parameters for a two- and five-band model, and solve these in dynamical-mean-field theory. The interaction-to-bandwidth ratio makes LK-99 a Mott or charge transfer insulator. Electron or hole doping (which is different from substituting Pb by Cu and thus differs from LK-99) is required to make it metallic and potentially superconducting.

Optimizing Superconductivity: From Cuprates via Nickelates to Palladates.

Motivated by cuprate and nickelate superconductors, we perform a comprehensive study of the superconducting instability in the single-band Hubbard model. We calculate the spectrum and superconducting transition temperature T_{c} as a function of filling and Coulomb interaction for a range of hopping parameters, using the dynamical vertex approximation. We find the sweet spot for high T_{c} to be at intermediate coupling, moderate Fermi surface warping, and low hole doping. Combining these results with first principles calculations, neither nickelates nor cuprates are close to this optimum within the single-band description. Instead, we identify some palladates, notably RbSr_{2}PdO_{3} and A_{2}^{'}PdO_{2}Cl_{2} (A^{'}=Ba_{0.5}La_{0.5}), to be virtually optimal, while others, such as NdPdO_{2}, are too weakly correlated.

Coulomb engineering of two-dimensional Mott materials.

Two-dimensional materials can be strongly influenced by their surroundings. A dielectric environment screens and reduces the Coulomb interaction between electrons in the two-dimensional material. Since in Mott materials the Coulomb interaction is responsible for the insulating state, manipulating the dielectric screening provides direct control over Mottness. Our many-body calculations reveal the spectroscopic fingerprints of such Coulomb engineering: we demonstrate eV-scale changes to the position of the Hubbard bands and show a Coulomb engineered insulator-to-metal transition. Based on our proof-of-principle calculations, we discuss the (feasible) conditions under which our scenario of Coulomb engineering of Mott materials can be realized experimentally.

Breaking of Thermopower-Conductivity Trade-Off in LaTiO3 Film around Mott Insulator to Metal Transition.

Introducing artificial strain in epitaxial thin films is an effective strategy to alter electronic structures of transition metal oxides (TMOs) and to induce novel phenomena and functionalities not realized in bulk crystals. This study reports a breaking of the conventional trade-off relation in thermopower (S)-conductivity (σ) and demonstrates a 2 orders of magnitude enhancement of power factor (PF) in compressively strained LaTiO3 (LTO) films. By varying substrates and reducing film thickness down to 4 nm, the out-of-plane to the in-plane lattice parameter ratio is controlled from 0.992 (tensile strain) to 1.034 (compressive strain). This tuning induces the electronic structure change from a Mott insulator to a metal and leads to a 103 -fold increase in σ up to 2920 S cm-1 . Concomitantly, the sign of S inverts from positive to negative, and both σ and S increase and break the trade-off relation between them in the n-type region. As a result, the PF (=S2 σ) is significantly enhanced to 300 µW m- 1 K-2 , which is 102 times larger than that of bulk LTO. Present results propose epitaxial strain as a means to finely tune strongly correlated TMOs close to their Mott transition, and thus to harness the hidden large thermoelectric PF.

Large phonon drag thermopower boosted by massive electrons and phonon leaking in LaAlO3/LaNiO3/LaAlO3 heterostructure.

An unusually large thermopower (S) enhancement is induced by heterostructuring thin films of the strongly correlated electron oxide LaNiO3. The phonon-drag effect, which is not observed in bulk LaNiO3, enhances S for thin films compressively strained by LaAlO3 substrates. By a reduction in the layer thickness down to three unit cells and subsequent LaAlO3 surface termination, a 10 times S enhancement over the bulk value is observed due to large phonon drag S (Sg), and the Sg contribution to the total S occurs over a much wider temperature range up to 220 K. The Sg enhancement originates from the coupling of lattice vibration to the d electrons with large effective mass in the compressively strained ultrathin LaNiO3, and the electron-phonon interaction is largely enhanced by the phonon leakage from the LaAlO3 substrate and the capping layer. The transition-metal oxide heterostructures emerge as a new playground to manipulate electronic and phononic properties in the quest for high-performance thermoelectrics.

Designing a mechanically driven spin-crossover molecular switch via organic embedding.

Among spin-crossover complexes, Fe-porphyrin (FeP) stands out for molecular spintronic applications: an intricate, yet favourable balance between ligand fields, charge transfer, and the Coulomb interaction makes FeP highly manipulable, while its planar structure facilitates device integration. Here, we theoretically design a mechanical spin-switch device in which external strain triggers the intrinsic magneto-structural coupling of FeP through a purely organic embedding. Exploiting the chemical compatibility and stretchability of graphene nanoribbon electrodes, we overcome common reliability and reproducibility issues of conventional inorganic setups. The competition between the Coulomb interaction and distortion-induced changes in ligand fields requires methodologies beyond the state-of-the-art: combining density functional theory with many-body techniques, we demonstrate experimentally feasible tensile strain to trigger a low-spin (S = 1) to high-spin (S = 2) crossover. Concomitantly, the current through the device toggles by over an order of magnitude, adding a fully planar mechanical current-switch unit to the panoply of molecular spintronics.

Topotactic Hydrogen in Nickelate Superconductors and Akin Infinite-Layer Oxides ABO_{2}.

Superconducting nickelates appear to be difficult to synthesize. Since the chemical reduction of ABO_{3} [rare earth (A), transition metal (B)] with CaH_{2} may result in both ABO_{2} and ABO_{2}H, we calculate the topotactic H binding energy by density functional theory (DFT). We find intercalating H to be energetically favorable for LaNiO_{2} but not for Sr-doped NdNiO_{2}. This has dramatic consequences for the electronic structure as determined by DFT+dynamical mean field theory: that of 3d^{9} LaNiO_{2} is similar to (doped) cuprates, 3d^{8} LaNiO_{2}H is a two-orbital Mott insulator. Topotactic H might hence explain why some nickelates are superconducting and others are not.

Thermoelectricity in correlated narrow-gap semiconductors.

We review many-body effects, their microscopic origin, as well as their impact on thermoelectricity in correlated narrow-gap semiconductors. Members of this class-such as FeSi and FeSb2-display an unusual temperature dependence in various observables: insulating with large thermopowers at low temperatures, they turn bad metals at temperatures much smaller than the size of their gaps. This insulator-to-metal crossover is accompanied by spectral weight-transfers over large energies in the optical conductivity and by a gradual transition from activated to Curie-Weiss-like behaviour in the magnetic susceptibility. We show a retrospective of the understanding of these phenomena, discuss the relation to heavy-fermion Kondo insulators-such as Ce3Bi4Pt3 for which we present new results-and propose a general classification of paramagnetic insulators. From the latter, FeSi emerges as an orbital-selective Kondo insulator. Focussing on intermetallics such as silicides, antimonides, skutterudites, and Heusler compounds we showcase successes and challenges for the realistic simulation of transport properties in the presence of electronic correlations. Further, we explore new avenues in which electronic correlations may contribute to the improvement of thermoelectric performance.

Electronics with Correlated Oxides: SrVO(3)/SrTiO(3) as a Mott Transistor.

We employ density functional theory plus dynamical mean field theory and identify the physical origin of why two layers of SrVO(3) on a SrTiO(3) substrate are insulating: the thin film geometry lifts the orbital degeneracy, which in turn triggers a first-order Mott-Hubbard transition. Two layers of SrVO(3) are just at the verge of a Mott-Hubbard transition and hence ideally suited for technological applications of the Mott-Hubbard transition: the heterostructure is highly sensitive to strain, electric field, and temperature. A gate voltage can also switch between metal (ON) and insulator (OFF), so that a transistor with ideal ON-OFF switching properties is realized.

Large Seebeck effect by charge-mobility engineering.

The Seebeck effect describes the generation of an electric potential in a conducting solid exposed to a temperature gradient. In most cases, it is dominated by an energy-dependent electronic density of states at the Fermi level, in line with the prevalent efforts towards superior thermoelectrics through the engineering of electronic structure. Here we demonstrate an alternative source for the Seebeck effect based on charge-carrier relaxation: a charge mobility that changes rapidly with temperature can result in a sizeable addition to the Seebeck coefficient. This new Seebeck source is demonstrated explicitly for Ni-doped CoSb3, where a marked mobility change occurs due to the crossover between two different charge-relaxation regimes. Our findings unveil the origin of pronounced features in the Seebeck coefficient of many other elusive materials characterized by a significant mobility mismatch. When utilized appropriately, this effect can also provide a novel route to the design of improved thermoelectric materials.

Dynamical correlations and screened exchange on the experimental bench: spectral properties of the cobalt pnictide BaCo2As2.

Understanding the Fermi surface and low-energy excitations of iron or cobalt pnictides is crucial for assessing electronic instabilities such as magnetic or superconducting states. Here, we propose and implement a new approach to compute the low-energy properties of correlated electron materials, taking into account both screened exchange beyond the local density approximation and local dynamical correlations. The scheme allows us to resolve the puzzle of BaCo2As2, for which standard electronic structure techniques predict a ferromagnetic instability not observed in nature.

Rare-earth vs. heavy metal pigments and their colors from first principles.

Many inorganic pigments contain heavy metals hazardous to health and environment. Much attention has been devoted to the quest for nontoxic alternatives based on rare-earth elements. However, the computation of colors from first principles is a challenge to electronic structure methods, especially for materials with localized f-orbitals. Here, starting from atomic positions only, we compute the colors of the red pigment cerium fluorosulfide as well as mercury sulfide (classic vermilion). Our methodology uses many-body theories to compute the optical absorption combined with an intermediate length-scale modelization to assess how coloration depends on film thickness, pigment concentration, and granularity. We introduce a quantitative criterion for the performance of a pigment. While for mercury sulfide, this criterion is satisfied because of large transition matrix elements between wide bands, cerium fluorosulfide presents an alternative paradigm: the bright red color is shown to stem from the combined effect of the quasi-2D and the localized nature of states. Our work shows the power of modern computational methods, with implications for the theoretical design of materials with specific optical properties.

Signatures of electronic correlations in iron silicide.

The intermetallic FeSi exhibits an unusual temperature dependence in its electronic and magnetic degrees of freedom, epitomized by the cross-over from a low-temperature nonmagnetic semiconductor to a high-temperature paramagnetic metal with a Curie-Weiss-like susceptibility. Many proposals for this unconventional behavior have been advanced, yet a consensus remains elusive. Using realistic many-body calculations, we here reproduce the signatures of the metal-insulator cross-over in various observables: the spectral function, the optical conductivity, the spin susceptibility, and the Seebeck coefficient. Validated by quantitative agreement with experiment, we then address the underlying microscopic picture. We propose a new scenario in which FeSi is a band insulator at low temperatures and is metalized with increasing temperature through correlation induced incoherence. We explain that the emergent incoherence is linked to the unlocking of iron fluctuating moments, which are almost temperature independent at short timescales. Finally, we make explicit suggestions for improving the thermoelectric performance of FeSi based systems.

Many-body effects in iron pnictides and chalcogenides: nonlocal versus dynamic origin of effective masses.

We apply the quasiparticle self-consistent GW approximation (QSGW) to some of the iron pnictide and chalcogenide superconductors. We compute Fermi surfaces and density of states, and find excellent agreement with experiment, substantially improving over standard band-structure methods. Analyzing the QSGW self-energy we discuss nonlocal and dynamic contributions to effective masses. We present evidence that the two contributions are mostly separable, since the quasiparticle weight is found to be essentially independent of momentum. The main effect of nonlocality is captured by the static but nonlocal QSGW effective potential. Moreover, these nonlocal self-energy corrections, absent in, e.g., dynamical mean field theory, can be relatively large. We show, on the other hand, that QSGW only partially accounts for dynamic renormalizations at low energies. These findings suggest that QSGW combined with dynamical mean field theory will capture most of the many-body physics in the iron pnictides and chalcogenides.

Multi-orbital effects in optical properties of vanadium sesquioxide.

Vanadium sesquioxide, V(2)O(3), boasts a rich phase diagram whose description necessitates accounting for many-body Coulomb correlations. The spectral properties of this compound have been successfully addressed within dynamical mean field theory to the extent that results of recent angle-resolved photoemission experiments have been correctly predicted. While photoemission spectroscopy probes the occupied part of the one-particle spectrum, optical experiments measure transitions into empty states and thus provide complementary information. In this work, we focus on the optical properties of V(2)O(3) in its paramagnetic phases by employing our recently developed 'generalized Peierls approach'. We obtain results in overall satisfactory agreement with experiments. Further, we rationalize that the experimentally observed temperature dependence stems from the different coherence scales of the charge carriers involved.

Effective band structure of correlated materials: the case of VO(2).

Vanadium dioxide VO(2) and its metal-insulator transition at T = 340 K continue to receive considerable interest. The question whether the physics of the insulating low-temperature phase is dominated by the Mott or the Peierls scenario, i.e. by correlation or band effects, is still under debate. A recent cluster dynamical mean field theory calculation (Biermann et al 2005 Phys. Rev. Lett. 94 026404) suggests a combination of both effects, characterizing the transition as of a correlation-assisted Peierls type. In this paper we present a detailed analysis of the excitation spectrum of the insulating M1 phase of VO(2), based on this calculation. We implement a scheme to analytically continue self-energies from Matsubara to real frequencies, and study the physics of the strong interactions, as well as the corresponding changes with respect to the density functional theory band structure within the local density approximation (LDA). We find that in the M1 phase lifetime effects are rather negligible, indeed allowing for an effective band structure description. A frequency-independent but orbital-dependent potential, constructed as an approximation to the full cluster dynamical mean field self-energy, turns out to satisfactorily reproduce the fully interacting one-particle spectrum, acting as a scissors operator which pushes the a(1g) bonding and e(g)(π) bands apart and, thus, opens the gap.