Hyperbolic exciton polaritons in a van der Waals magnet.

Exciton polaritons are quasiparticles of photons coupled strongly to bound electron-hole pairs, manifesting as an anti-crossing light dispersion near an exciton resonance. Highly anisotropic semiconductors with opposite-signed permittivities along different crystal axes are predicted to host exotic modes inside the anti-crossing called hyperbolic exciton polaritons (HEPs), which confine light subdiffractionally with enhanced density of states. Here, we show observational evidence of steady-state HEPs in the van der Waals magnet chromium sulfide bromide (CrSBr) using a cryogenic near-infrared near-field microscope. At low temperatures, in the magnetically-ordered state, anisotropic exciton resonances sharpen, driving the permittivity negative along one crystal axis and enabling HEP propagation. We characterize HEP momentum and losses in CrSBr, also demonstrating coupling to excitonic sidebands and enhancement by magnetic order: which boosts exciton spectral weight via wavefunction delocalization. Our findings open new pathways to nanoscale manipulation of excitons and light, including routes to magnetic, nonlocal, and quantum polaritonics.

A theory for colors of strongly correlated electronic systems.

Many strongly correlated transition metal insulators are colored, even though they have band gaps much larger than the highest energy photons from the visible light. An adequate explanation for the color requires a theoretical approach able to compute subgap excitons in periodic crystals, reliably and without free parameters-a formidable challenge. The literature often fails to disentangle two important factors: what makes excitons form and what makes them optically bright. We pick two archetypal cases as examples: NiO with green color and MnF2 with pink color, and employ two kinds of ab initio many body Green's function theories; the first, a perturbative theory based on low-order extensions of the GW approximation, is able to explain the color in NiO, while the same theory is unable to explain why MnF2 is pink. We show its color originates from higher order spin-flip transitions that modify the optical response, which is contained in dynamical mean-field theory (DMFT). We show that symmetry lowering mechanisms may determine how 'bright' these excitons are, but they are not fundamental to their existence.

A Perspective on Sustainable Computational Chemistry Software Development and Integration.

The power of quantum chemistry to predict the ground and excited state properties of complex chemical systems has driven the development of computational quantum chemistry software, integrating advances in theory, applied mathematics, and computer science. The emergence of new computational paradigms associated with exascale technologies also poses significant challenges that require a flexible forward strategy to take full advantage of existing and forthcoming computational resources. In this context, the sustainability and interoperability of computational chemistry software development are among the most pressing issues. In this perspective, we discuss software infrastructure needs and investments with an eye to fully utilize exascale resources and provide unique computational tools for next-generation science problems and scientific discoveries.

Ultrafast Carrier and Lattice Dynamics in Plasmonic Nanocrystalline Copper Sulfide Films.

Excited carrier dynamics in plasmonic nanostructures determines many important optical properties such as nonlinear optical response and photocatalytic activity. Here it is shown that mesoscopic plasmonic covellite nanocrystals with low free-carrier concentration exhibit a much faster carrier relaxation than in traditional plasmonic materials. A nonequilibrium hot-carrier population thermalizes within first 20 fs after photoexcitation. A decreased thermalization time in nanocrystals compared to a bulk covellite is consistent with the reduced Coulomb screening in ultrathin films. The subsequent relaxation of thermalized, equilibrium electron gas is faster than in traditional plasmonic metals due to the lower carrier concentration and agrees well with that in a bulk covellite showing no evidence of quantum confinement or hot-hole trapping at the surface states. The excitation of coherent optical phonon modes in a covellite is also demonstrated, revealing coherent lattice dynamics in plasmonic materials, which until now was mainly limited to dielectrics, semiconductors, and semimetals. These findings show advantages of this new mesoscopic plasmonic material for active control of optical processes.

Controlling T_{c} through Band Structure and Correlation Engineering in Collapsed and Uncollapsed Phases of Iron Arsenides.

Recent observations of selective emergence (suppression) of superconductivity in the uncollapsed (collapsed) tetragonal phase of LaFe_{2}As_{2} has rekindled interest in understanding what features of the band structure control the superconducting T_{c}. We show that the proximity of the narrow Fe-d_{xy} state to the Fermi energy emerges as the primary factor. In the uncollapsed phase this state is at the Fermi energy, and is most strongly correlated and a source of enhanced scattering in both single and two particle channels. The resulting intense and broad low energy spin fluctuations suppress magnetic ordering and simultaneously provide glue for Cooper pair formation. In the collapsed tetragonal phase, the d_{xy} state is driven far below the Fermi energy, which suppresses the low-energy scattering and blocks superconductivity. A similar source of broad spin excitation appears in uncollapsed and collapsed phases of CaFe_{2}As_{2}. This suggests controlling coherence provides a way to engineer T_{c} in unconventional superconductors primarily mediated through spin fluctuations.

Electron-phonon-driven three-dimensional metallicity in an insulating cuprate.

The role of the crystal lattice for the electronic properties of cuprates and other high-temperature superconductors remains controversial despite decades of theoretical and experimental efforts. While the paradigm of strong electronic correlations suggests a purely electronic mechanism behind the insulator-to-metal transition, recently the mutual enhancement of the electron-electron and the electron-phonon interaction and its relevance to the formation of the ordered phases have also been emphasized. Here, we combine polarization-resolved ultrafast optical spectroscopy and state-of-the-art dynamical mean-field theory to show the importance of the crystal lattice in the breakdown of the correlated insulating state in an archetypal undoped cuprate. We identify signatures of electron-phonon coupling to specific fully symmetric optical modes during the buildup of a three-dimensional (3D) metallic state that follows charge photodoping. Calculations for coherently displaced crystal structures along the relevant phonon coordinates indicate that the insulating state is remarkably unstable toward metallization despite the seemingly large charge-transfer energy scale. This hitherto unobserved insulator-to-metal transition mediated by fully symmetric lattice modes can find extensive application in a plethora of correlated solids.

Anisotropic Plasmonic CuS Nanocrystals as a Natural Electronic Material with Hyperbolic Optical Dispersion.

Copper sulfide nanocrystals have recently been studied due to their metal-like behavior and strong plasmonic response, which make them an attractive material for nanophotonic applications in the near-infrared spectral range; however, the nature of the plasmonic response remains unclear. We have performed a combined experimental and theoretical study of the optical properties of copper sulfide colloidal nanocrystals and show that bulk CuS resembles a heavily doped p-type semiconductor with a very anisotropic energy band structure. As a consequence, CuS nanoparticles possess key properties of relevance to nanophotonics applications: they exhibit anisotropic plasmonic behavior in the infrared and support optical modes with hyperbolic dispersion in the 670-1050 nm spectral range. We also predict that the ohmic loss is low compared to conventional plasmonic materials such as noble metals in the NIR. The plasmonic resonances can be tuned by controlling the size and shape of the nanocrystals, providing a playground for future nanophotonic applications in the near-infrared.

Experimental and theoretical optical properties of methylammonium lead halide perovskites.

The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3](+) cations has a significant influence on the position of the bandgap suggesting that collective orientation of the organic moieties could result in significant local variations of the optical properties. The optical constants and energy band diagram of CH3NH3PbI3 are then used to simulate the contributions from different optical transitions to a typical transient absorption spectrum (TAS).

Atomistic origins of high-performance in hybrid halide perovskite solar cells.

The performance of organometallic perovskite solar cells has rapidly surpassed that of both conventional dye-sensitized and organic photovoltaics. High-power conversion efficiency can be realized in both mesoporous and thin-film device architectures. We address the origin of this success in the context of the materials chemistry and physics of the bulk perovskite as described by electronic structure calculations. In addition to the basic optoelectronic properties essential for an efficient photovoltaic device (spectrally suitable band gap, high optical absorption, low carrier effective masses), the materials are structurally and compositionally flexible. As we show, hybrid perovskites exhibit spontaneous electric polarization; we also suggest ways in which this can be tuned through judicious choice of the organic cation. The presence of ferroelectric domains will result in internal junctions that may aid separation of photoexcited electron and hole pairs, and reduction of recombination through segregation of charge carriers. The combination of high dielectric constant and low effective mass promotes both Wannier-Mott exciton separation and effective ionization of donor and acceptor defects. The photoferroic effect could be exploited in nanostructured films to generate a higher open circuit voltage and may contribute to the current-voltage hysteresis observed in perovskite solar cells.

On the Chemical Origin of the Gap Bowing in (GaAs)(1-x)Ge(2x) Alloys: A Combined DFT-QSGW Study.

Motivated by the research and analysis of new materials for photovoltaics and by the possibility of tailoring their optical properties for improved solar energy conversion, we have focused our attention on the (GaAs)(1-x)Ge(2x) series of alloys. We have investigated the structural properties of some (GaAs)(1-x)Ge(2x) compounds within the local-density approximation to density-functional theory, and their optical properties within the Quasiparticle Self-consistent GW approximation. The QSGW results confirm the experimental evidence of asymmetric bandgap bowing. It is explained in terms of violations of the octet rule, as well as in terms of the order-disorder phase transition.

Discovery of a novel linear-in-k spin splitting for holes in the 2D GaAs/AlAs system.

The spin-orbit interaction generally leads to spin splitting (SS) of electron and hole energy states in solids, a splitting that is characterized by a scaling with the wave vector k. Whereas for 3D bulk zinc blende solids the electron (heavy-hole) SS exhibits a cubic (linear) scaling with k, in 2D quantum wells, the electron (heavy-hole) SS is currently believed to have a mostly linear (cubic) scaling. Such expectations are based on using a small 3D envelope function basis set to describe 2D physics. By treating instead the 2D system explicitly as a system in its own right, we discover a large linear scaling of hole states in 2D. This scaling emerges from coupling of hole bands that would be unsuspected by the standard model that judges coupling by energy proximity. This discovery of a linear Dresselhaus k scaling for holes in 2D implies a different understanding of hole physics in low dimensions.

Tunneling anisotropic magnetoresistance driven by resonant surface states: first-principles calculations on an Fe(001) surface.

Fully relativistic first-principles calculations of the Fe(001) surface demonstrate that resonant surface (interface) states may produce sizable tunneling anisotropic magnetoresistance in magnetic tunnel junctions with a single magnetic electrode. The effect is driven by the spin-orbit coupling. It shifts the resonant surface band via the Rashba effect when the magnetization direction changes. We find that spin-flip scattering at the interface is controlled not only by the strength of the spin-orbit coupling, but depends strongly on the intrinsic width of the resonant surface states.

Reversal of spin polarization in Fe/GaAs (001) driven by resonant surface states: first-principles calculations.

A minority-spin resonant state at the Fe/GaAs(001) interface is predicted to reverse the spin polarization with the voltage bias of electrons transmitted across this interface. Using a Green's function approach within the local spin-density approximation, we calculate the spin-dependent current in a Fe/GaAs/Cu tunnel junction as a function of the applied bias voltage. We find a change in sign of the spin polarization of tunneling electrons with bias voltage due to the interface minority-spin resonance. This result explains recent experimental data on spin injection in Fe/GaAs contacts and on tunneling magnetoresistance in Fe/GaAs/Fe magnetic tunnel junctions.

Breakdown of a gold nanowire between electrodes.

Deformation behavior of an atomic Au wire placed between Au electrodes was investigated by using a generalization of the method of linear muffin-tin orbitals (LMTO) within the local-density approximation (LDA). We studied the dynamical motion of the atoms in the wire. Soft phonon modes were studied. It has been found that collective motions are dominated by motions perpendicular to the wire axis. Large displacements which resulted in wire breakage were also studied. The energy barrier associated with this process has been calculated.

Ab initio prediction of conduction band spin splitting in zinc blende semiconductors.

We use a recently developed self-consistent GW approximation to present systematic ab initio calculations of the conduction band spin splitting in III-V and II-VI zinc blende semiconductors. The spin-orbit interaction is taken into account as a perturbation to the scalar relativistic Hamiltonian. These are the first calculations of conduction band spin splittings based on a quasiparticle approach; and because the self-consistent GW scheme accurately reproduces the relevant band parameters, it is expected to be a reliable predictor of spin splittings. The results are compared to the few available experimental data and a previous calculation based on a model one-particle potential. We also briefly address the widely used k x p parametrization in the context of these results.

Density-functional calculation of CeO2 surfaces and prediction of effects of oxygen partial pressure and temperature on stabilities.

We have used density-functional theory to investigate (111), (110), (210), (211), (100), and (310) surfaces of ceria (CeO2). Compared with previous interatomic-potential-based studies, our calculations reported a slightly different relative stability ordering and significantly lower surface energies for the stoichiometric surfaces. Using a defect model, the surface stabilities were evaluated as functions of oxygen partial pressure and temperature. Our investigations were restricted to ideal surface terminations, without considering defect formation on those surfaces. We found that at 300 K, the stoichiometric (111) has the lowest free energy for a wide range of oxygen partial pressures up to 1 atm, and only at ultrahigh vacuum does the Ce-terminated (111) becomes the most stable one. The transition point for the Ce-terminated (111) surfaces moves to higher oxygen partial pressures when temperature increases. To improve the prediction of electron density of states, we used the local-density approximation plus U(J) correction method to correct the on-site Coulomb correlation and exchange interaction due to the strongly localized Ce-4f electrons. The optimal parameter combination of U = 7 eV and J = 0.7 eV was found to improve the O 2p-Ce 4f gap without much degradation of ground-state bulk properties or the O 2p-Ce 5d gap. The bulk and surface electronic structures were then analyzed based on the improved density of states.

All-electron self-consistent GW approximation: application to Si, MnO, and NiO.

We present a new kind of self-consistent GW approximation based on the all-electron, full-potential linear muffin-tin orbital method. By iterating the eigenfunctions of the GW Hamiltonian, self-consistency in both the charge density and the quasiparticle spectrum is achieved. We explain why this form of self-consistency should be preferred to the conventional one. Some results for Si (a representative semiconductor) are presented. Finally we consider many details in the electronic structure of the antiferromagnetic insulators MnO and NiO. Excellent agreement with experiment is shown for many properties, suggesting that a Landau quasiparticle (energy band) picture provides a reasonable description of electronic structure even in these correlated materials.

Understanding the magnetocatalytic effect: magnetism as a driving force for surface segregation.

The magnetocatalytic (or Hedvall) effect refers to a change in the rate of a chemical reaction on a magnetic surface at the Curie point T(C). For Ni catalysts, experiments suggest the effect is related to a sudden increase in segregated surface C, a strong catalytic poison, at temperatures below T(C). However, the connection between magnetism and surface segregation is not understood. Using density functional theory and spin-dynamics simulations, we show that the solubility of C in Ni is significantly reduced in the ferromagnetic state, because C suppresses Ni magnetism and thereby increases the heat of solution. This explains the observed increase in C segregation and the reduced catalytic activity below T(C).