Table of contents

Alkali-doped fullerides (${{A}_{3}}{{\text{C}}_{60}}$ with A  =  K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature (${{T}_{\text{c}}}$) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-${{T}_{\text{c}}}$ superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron–phonon coupling and the electron–electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn–Teller phonons and Hund's coupling within the ${{\text{C}}_{60}}$ molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn–Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-${{T}_{\text{c}}}$ superconductivity.

Recent remarkable progress in angle-resolved photoelectron spectroscopy (ARPES) has enabled the direct observation of the band structures of 4f and 5f materials. In particular, ARPES with various light sources such as lasers ($h\nu \sim 7~\text{eV}$) or high-energy synchrotron radiations ($h\nu \gtrsim 400~\text{eV}$) has shed light on the bulk band structures of strongly correlated materials with energy scales of a few millielectronvolts to several electronvolts. The purpose of this paper is to summarize the behaviors of 4f and 5f band structures of various rare-earth and actinide materials observed by modern ARPES techniques, and understand how they can be described using various theoretical frameworks. For 4f-electron materials, ARPES studies of $\text{Ce}M\text{I}{{\text{n}}_{5}}$ ($M=\text{Rh}$, $\text{Ir}$, and $\text{Co}$) and $\text{YbR}{{\text{h}}_{2}}\text{S}{{\text{i}}_{2}}$ with various incident photon energies are summarized. We demonstrate that their 4f electronic structures are essentially described within the framework of the periodic Anderson model, and that the band-structure calculation based on the local density approximation cannot explain their low-energy electronic structures. Meanwhile, electronic structures of 5f materials exhibit wide varieties ranging from itinerant to localized states. For itinerant $\text{U}~5f$ compounds such as $\text{UFeG}{{\text{a}}_{5}}$, their electronic structures can be well-described by the band-structure calculation assuming that all $\text{U}~5f$ electrons are itinerant. In contrast, the band structures of localized $\text{U}~5f$ compounds such as $\text{UP}{{\text{d}}_{3}}$ and $\text{U}{{\text{O}}_{2}}$ are essentially explained by the localized model that treats $\text{U}~5f$ electrons as localized core states. In regards to heavy fermion $\text{U}$-based compounds such as the hidden-order compound $\text{UR}{{\text{u}}_{2}}\text{S}{{\text{i}}_{2}}$, their electronic structures exhibit complex behaviors. Their overall band structures are generally well-explained by the band-structure calculation, whereas the states in the vicinity of E_F show some deviations due to electron correlation effects. Furthermore, the electronic structures of $\text{UR}{{\text{u}}_{2}}\text{S}{{\text{i}}_{2}}$ in the paramagnetic and hidden-order phases are summarized based on various ARPES studies. The present status of the field as well as possible future directions are also discussed.

Quantum effects that arise from confinement of electronic states have been extensively studied for the surface states of noble metals. Utilizing small artificial structures for confinement allows tailoring of the surface properties and offers unique opportunities for applications. So far, examples of surface state confinement include thin films, artificial nanoscale structures, vacancy and adatom islands, self-assembled 1D chains, vicinal surfaces, quantum dots and quantum corrals. In this review we summarize recent achievements in changing the electronic structure of surfaces by adsorption of nanoporous networks whose design principles are based on the concepts of supramolecular chemistry. Already in 1993, it was shown that quantum corrals made from Fe atoms on a Cu(1 1 1) surface using single atom manipulation with a scanning tunnelling microscope confine the Shockley surface state. However, since the atom manipulation technique for the construction of corral structures is a relatively time consuming process, the fabrication of periodic two-dimensional (2D) corral structures is practically impossible. On the other side, by using molecular self-assembly extended 2D porous structures can be achieved in a parallel process, i.e. all pores are formed at the same time. The molecular building blocks are usually held together by non-covalent interactions like hydrogen bonding, metal coordination or dipolar coupling. Due to the reversibility of the bond formation defect-free and long-range ordered networks can be achieved. However, recently also examples of porous networks formed by covalent coupling on the surface have been reported. By the choice of the molecular building blocks, the dimensions of the network (pore size and pore to pore distance) can be controlled. In this way, the confinement properties of the individual pores can be tuned. In addition, the effect of the confined state on the hosting properties of the pores will be discussed in this review article.

Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager's reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

Vacancy-mediated diffusion of an Al atom in the pure Mg matrix is studied using the atomistic, on-lattice self-learning kinetic Monte Carlo (SLKMC) method. Activation barriers for vacancy-Mg and vacancy-Al atom exchange processes are calculated on the fly using the climbing image nudged-elastic-band method and binary Mg–Al modified embedded-atom method interatomic potential. Diffusivities of an Al atom obtained from SLKMC simulations show the same behavior as observed in experimental and theoretical studies available in the literature; that is, an Al atom diffuses faster within the basal plane than along the c-axis. Although the effective activation barriers for an Al atom diffusion from SLKMC simulations are close to experimental and theoretical values, the effective prefactors are lower than those obtained from experiments. We present all the possible vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers identified in SLKMC simulations. A simple mapping scheme to map an HCP lattice onto a simple cubic lattice is described, which enables simulation of the HCP lattice using the on-lattice framework. We also present the pattern recognition scheme which is used in SLKMC simulations to identify the local Al atom configuration around a vacancy.

Bloch oscillations of electrons are shown to occur for cases when the energy spectrum does not consist of the traditional evenly-spaced ladders and the potential gradient does not result from an external electric field. A theory of such generalized Bloch oscillations is presented and an exact calculation is given to confirm this phenomenon. Our results allow for a greater freedom of design for experimentally observing Bloch oscillations. For strongly coupled oscillator systems displaying Bloch oscillations, it is further demonstrated that reordering of oscillators leads to destruction of Bloch oscillations. We stipulate that the presented theory of generalized Bloch oscillations can be extended to other systems such as acoustics and photonics.

Plasmonic resonance of a metallic nanostructure results from coherent motion of its conduction electrons driven by incident light. At the resonance, the induced dipole in the nanostructure is proportional to the number of the conduction electrons, hence 10⁷ times larger than that in an atom. The interaction energy between the induced dipole and fluctuating virtual field of the incident light can reach a few tenths of an eV. Therefore, the classical electromagnetism dominating the field may become inadequate. We propose that quantum electrodynamics (QED) may be used as a fundamental theory to describe the interaction between the virtual field and the oscillating electrons. Based on QED, we derive analytic expressions for the plasmon resonant frequency, which depends on three easily accessible material parameters. The analytic theory reproduces very well the experimental data, and can be used in rational design of materials for plasmonic applications.

One of the most widely used x-ray standards and a highly applied component of catalysis systems, CeO₂ has been studied for the purpose of better understanding its equation of state and electronic properties. Diamond anvil cells have been used to extend the equation of state for this material to 130 GPa and explore the electronic behavior with applied load. From the x-ray diffraction studies, it has been determined that the high pressure phase transition extends from approximately 35–75 GPa at ambient temperature. Elevation of temperature is found to decrease the initiation pressure for this transition, with multiple distinct temperature regions which indicate structural related anomalies. In addition, hydrostatic and non-hydrostatic effects are compared and exhibit a drastic difference in bulk moduli. The electronic results indicate a change in the scattering environment of the cerium atom, associated with the high pressure phase transition. Overall, these results present the first megabar pressure study and the first high pressure and temperature study of ceria. Additionally, this shows the first combined study of the K and L_III edges of this material to 33 GPa.

We report a theoretical study of electron spin resonance in bulk topological insulators, such as Bi₂Se₃, Bi₂Te₃ and Sb₂Te₃. Using the effective four-band model, we find the electron energy spectrum in a static magnetic field and determine the response to electric and magnetic dipole perturbations, represented by oscillating electric and magnetic fields perpendicular to the static field. We determine the associated selection rules and calculate the absorption spectra. This enables us to separate the effective orbital and spin degrees of freedom and to determine the effective g factors for electrons and holes.

The electronic structure for the conduction bands of both hexagonal and orthorhombic LuFeO₃ thin films have been measured using x-ray absorption spectroscopy at oxygen K (O K) edge. Dramatic differences in both the spectral features and the linear dichroism are observed. These differences in the spectra can be explained using the differences in crystal field splitting of the metal (Fe and Lu) electronic states and the differences in O 2p-Fe 3d and O 2p-Lu 5d hybridizations. While the oxidation states have not changed, the spectra are sensitive to the changes in the local environments of the Fe³⁺ and Lu³⁺ sites in the hexagonal and orthorhombic structures. Using the crystal-field splitting and the hybridizations that are extracted from the measured electronic structures and the structural distortion information, we derived the occupancies of the spin minority states in Fe³⁺, which are non-zero and uneven. The single ion anisotropy on Fe³⁺ sites is found to originate from these uneven occupancies of the spin minority states via spin–orbit coupling in LuFeO₃.

Understanding the nature and characteristics of the intrinsic defects and impurities in the dielectric barrier separating the ferromagnetic electrodes in a magnetic tunneling junction is of great importance for understanding the often observed 'barrier-breakdown' therein. In this connection, we present herein systematic experimental (SQUID and synchrotron-radiation-based x-ray absorption spectroscopy) and computational studies on the electronic and magnetic properties of Mg_1−xFe_xO thin films. Our studies reveal: (i) defect aggregates comprised of basic and trimer units (Fe impurity coupled to 1 or 2 Mg vacancies) and (ii) existence of two competing magnetic orders, defect- and dopant-induced, with spin densities aligning anti-parallel if the trimer is present in the oxide matrix. These findings open up new avenues for designing tunneling barriers with high endurance and tunneling effect upon tuning the concentration/distribution of the two magnetic orders.

We present a systematic first-principles study of Fe | MgO bilayer systems emphasizing the influence of the iron layer thickness on the geometry, the electronic structure and the magnetic properties. Our calculations ensure the unconstrained structural relaxation at scalar relativistic level for various numbers of iron layers placed on the magnesium oxide substrate. Our results show that due to the formation of the interface the electronic structure of the interface iron atoms is significantly modified involving charge transfer within the iron subsystem. In addition, we find that the magnetic anisotropy energy increases from 1.9 mJ m⁻² for 3 Fe layers up to 3.0 mJ m⁻² for 11 Fe layers.