We study the electronic structure and correlated phases of twisted bilayers of platinum diselenide using large-scale ab initio simulations combined with the functional renormalization group. PtSe2 is a group-X transition metal dichalcogenide, which hosts emergent flat bands at small twist angles in the twisted bilayer. Remarkably, we find that Moiré engineering can be used to tune the strength of Rashba spin–orbit interactions, altering the electronic behavior in a novel manner. We reveal that an effective triangular lattice with a twist-controlled ratio between kinetic and spin–orbit coupling (SOC) scales can be realized. Even dominant SOC can be accessed in this way and we discuss consequences for the interaction driven phase diagram, which features pronounced exotic superconducting and entangled spin-charge density waves.

We present the idea and illustrate potential benefits of having a tool chain of closely related regular, unscreened and screened hybrid exchange–correlation (XC) functionals, all within the consistent formulation of the van der Waals density functional (vdW-DF) method (Hyldgaard et al (2020 J. Phys.: Condens. Matter 32 393001)). Use of this chain of nonempirical XC functionals allows us to map when the inclusion of truly nonlocal exchange and of truly nonlocal correlation is important. Here we begin the mapping by addressing hard and soft material challenges: magnetic elements, perovskites, and biomolecular problems. We also predict the structure and polarization for a ferroelectric polymer. To facilitate this work and future broader explorations, we present a stress formulation for spin vdW-DF and illustrate the use of a simple stability-modeling scheme. The modeling supplements density functional theory (DFT) (with a specific XC functional) by asserting whether the finding of a soft mode (an imaginary-frequency vibrational mode, ubiquitous in perovskites and soft matter) implies an actual DFT-based prediction of a low-temperature transformation.

Hybridization effects play a crucial role in determining the electronic properties of hybrid inorganic/organic interfaces. To gain insight into these important interactions, we perform a first-principles study based on hybrid density-functional theory including spin–orbit coupling, focusing on eight representative systems formed by two carbon-conjugated molecules—pyrene and perylene—physisorbed on the transition-metal dichalcogenide monolayers (TMDCs) MoS2, MoSe2, WS2, and WSe2. By means of band unfolding techniques, we analyze the band structures of the considered materials, identifying the contributions of the individual constituents as well as the signatures of their hybridization. Based on symmetry and energetic arguments, we derive general conditions for electronic hybridization between conjugated molecules and underlying TMDCs even when the former do not lie planar on the latter, thus providing the key to predict how their mutual arrangement affect their electronic interactions.

Recently a novel approach to find approximate exchange–correlation functionals in density-functional theory was presented (Mordovina et al 2019 J. Chem. Theory Comput. 15 5209), which relies on approximations to the interacting wave function using density-matrix embedding theory (DMET). This approximate interacting wave function is constructed by using a projection determined by an iterative procedure that makes parts of the reduced density matrix of an auxiliary system the same as the approximate interacting density matrix. If only the diagonal of both systems are connected this leads to an approximation of the interacting-to-non-interacting mapping of the Kohn–Sham approach to density-functional theory. Yet other choices are possible and allow to connect DMET with other density-functional theories such as kinetic-energy density functional theory or reduced density-matrix functional theory. In this work we give a detailed review of the basics of the DMET procedure from a density-functional perspective and show how both approaches can be used to supplement each other. We do not present a specific realization of combining density-functional methods with DMET but rather provide common grounds to facilitate future developments that encompass both approaches. We do so explicitly for the case of a one-dimensional lattice system, as this is the simplest setting where we can apply DMET and the one that was originally presented. Among others we highlight how the mappings of density-functional theories can be used to identify uniquely defined auxiliary systems and projections in DMET and how to construct approximations for different density-functional theories using DMET inspired projections. Such alternative approximation strategies become especially important for density-functional theories that are based on non-linearly coupled observables such as kinetic-energy density-functional theory, where the Kohn–Sham fields are no longer obtainable by functional differentiation of an energy expression, or for reduced density-matrix functional theories, where a straightforward Kohn–Sham construction is not feasible.

We have studied the accuracy of 16 different density functional theory methods to reproduce experimental data for bond lengths, angles, vibrational frequencies, as well as enthalpies and entropies for the binding of N2, H2, CO and hydride ions to various transition-metal complexes (with Fe, Ni, Cr, Mo and W) with relation to nitrogenase. We show that generalized gradient approximation functionals give better structure-related parameters, whereas hybrid functionals often give better energies. However, the BLYP and B97D functionals seem to give reasonably accurate results for both types of properties. Geometries and entropies are converged with split-valence basis sets, but energies and vibrational frequencies (and therefore also thermal corrections) in general require a basis set of triple-zeta quality. Dispersion corrections are important to obtain accurate energies (contributing by up to 57 kJ mol−1), as well as structures.

The linear augmented-Slater-type-orbital (LASTO) method, as one of real-space band theories, is generalized to a spin-polarized Dirac-type density-functional in full potential scheme. Since the Bloch sum of Slater-type orbital can do the Fourier transformation analytically with a conditional convergence, it is not only easily extendable to a full-potential scheme, but also have a high compatibility to a four-component relativistic linear-augmented-plane-wave method. In this paper, the formulation of this full potential Dirac-type LASTO (DLASTO) method is presented in a self-contained manner. By applying it to a typical material for each of the 3d-, 4f- and 5f-electron systems, we discuss some of the cut-off parameters and orbital choices required in the DLASTO calculation and provide guidelines for their settings. In addition, the electronic structure and magnetism for each of these systems will be discussed.

High performance computing is a powerful tool to accelerate the Kohn–Sham density functional theory calculations on modern heterogeneous supercomputers. Here, we describe a massively parallel implementation of large-scale linear-response time-dependent density functional theory (LR-TDDFT) to calculate the excitation energies and wave functions of solids with plane-wave basis set. We adopt a two-level parallelization strategy that combines the message passing interface with open multi-processing parallel programming to deal with the matrix operations and data communications of constructing and diagonalizing the LR-TDDFT Hamiltonian matrix. Numerical results illustrate that the LR-TDDFT calculations can scale up to 24 576 processing cores on modern heterogeneous supercomputers to study the excited state properties of bulky silicon systems containing thousands of atoms (4,096 atoms). We demonstrate that the LR-TDDFT calculations can be used to investigate the photoinduced charge separation of water molecule adsorption on rutile TiO2(110) surface from an excitonic perspective.

The electronic structures of layered rare-earth tritelluride RTe3 (R = Pr, Er) charge density wave (CDW) compounds have been investigated by performing R 4d → 4f resonant photoemission spectroscopy (RPES) and angle-resolved photoemission spectroscopy (ARPES) measurements for high-quality single crystals. R 4d → 4f RPES measurements reveal that the R 4f states do not contribute directly to the CDW formation in RTe3 but that the R 4f-Te 5p hybridization in PrTe3 is significantly larger than that in ErTe3. In the photon-energy maps for the Fermi-edge (E F)-crossing states in RTe3, straight vertical dispersions are observed along k c , demonstrating the 2D character for the near-E F states in both R = Pr and Er. This finding implies the weak interlayer interaction between R-Te(1) and Te(2)–Te(3) layers, which is supported by the similar linear dichroism in ARPES for PrTe3 and ErTe3. The CDW-induced Fermi surface of PrTe3 exhibits two-fold symmetric features while that of ErTe3 exhibits four-fold symmetric features. This finding reveals different CDW distortions in PrTe3 and ErTe3, the origin of which is likely to be different ionic sizes of R ions and different R 4f-Te 5p hybridization.

The three-dimensional (3D) electronic structure of the hidden order compound URu2Si2 in a paramagnetic phase was revealed using a 3D angle-resolved photoelectron spectroscopy where the electronic structure of the entire Brillouin zone is obtained by scanning both incident photon energy and detection angles of photoelectrons. The quasi-particle bands with enhanced contribution from the U 5f state were observed near E F, formed by the hybridization with the Ru 4d states. The energy dispersion of the quasi-particle band is significantly depend on k z , indicating that they inherently have a 3D nature. The band-structure calculation qualitatively explain the characteristic features of the band structure and Fermi surface although the electron correlation effect strongly renormalizes the quasi-particle bands. The 3D and strongly-correlated nature of the quasi-particle bands in URu2Si2 is an essential ingredient for modeling its hidden-order transition.

Nature’s photosynthetic machinery uses precisely arranged pigment-protein complexes, often representing superstructures, for efficient light-harvesting and transport of excitation energy (excitons) during the initial steps of photosynthesis. This function is achieved by defined electronic Coulomb interactions between the conjugated molecules resulting in tailored excited-state energy landscapes. While such complex natural structures are synthetically difficult to achieve, supramolecular chemistry is now on its advent to realize defined artificial supramolecular nanostructures with tailored functionalities via controlled self-assembly processes of small molecules. In this review, we focus on recent work reporting photophysical studies on self-assembled and hierarchical nanostructures as well as complex superstructures. We discuss how the resulting excited-state energy landscapes influence energy transport. Progress in the field of supramolecular chemistry allows for the realization of distinct kinds of H- or J-aggregates with well-defined morphologies on the mesoscale. Advances in the field of optical spectroscopy and microscopy have permitted to resolve the incoherent/coherent dynamics of exciton transport in such systems down to the level of single nanostructures. Although outstanding diffusion lengths of up to several μm were found in selected nanostructures, a full understanding of the underlying principles is still missing. In particular, the unavoidable structural and electronic disorder in these systems influences the excited-state energy landscapes and thus the transport characteristics, which can be exploited to refine the molecular design criteria of supramolecular nanostructures and complex superstructures. Despite the rapid progress in the field of functional supramolecular nanostructures, we believe that revealing the full potential of such systems is far from complete. In particular, criteria for tailored and optimized (hierarchical) supramolecular nanostructures in view of applications are not yet established. Finally, we outline current challenges and future perspectives for optical and optoelectronic applications of supramolecular nanostructures.