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The emerging interest in two-dimensional electron gases (2DEGs), formed at interfaces between two insulating oxide perovskites, poses a crucial fundamental question in view of future electronic devices. In the framework of density-functional theory, we investigate the possibility to control the characteristics of the 2DEG formed at the LaInO 3 /BaSnO 3 interface by including a ferroelectric layer. To do so, we consider BaTiO 3 as a prototype example and examine how the orientation of the ferroelectric polarization impacts density and confinement of the 2DEG. We find that aligning the ferroelectric polarization toward (outward) the LaInO 3 /BaSnO 3 interface leads to an accumulation (depletion) of the interfacial 2DEG. Varying its magnitude, we find a linear effect on the 2DEG charge density that is confined within the BaSnO 3 side. Analysis of the optimized geometries reveals that inclusion of the ferroelectric layer makes structural distortions at the LaInO 3 /BaSnO 3 junction less pronounced, which, in turn, enhances the 2DEG density. Thicker ferroelectric layers allow for reaching higher polarization magnitude. We discuss the mechanisms behind all these findings and rationalize how the characteristics of both 2DEGs and 2D hole gases can be controlled in the considered heterostructures. Overall, our results can be generalized to other combinations of ferroelectric, polar, and nonpolar materials.

By enabling control of valley degrees of freedom in transition-metal dichalcogenides, valley-selective circular dichroism has become a key concept in valleytronics. Herein, we show that valley excitons, bound electron-hole pairs formed at the K or K̅ valleys upon absorption of circularly polarized light, are chiral quasiparticles characterized by a finite orbital angular momentum (OAM). We further formulate an ab initio many-body theory of valley-selective circular dichroism and valley excitons based on the Bethe-Salpeter equation. Besides governing the interaction with circularly polarized light, the OAM confers upon excitons a finite magnetization that manifests itself through an excitonic Zeeman splitting upon interaction with external magnetic fields. The good agreement between our ab initio calculations and recent experimental measurements of the exciton Zeeman shifts corroborates this picture, indicating that valley excitons can carry angular momentum even in their singlet state.

We combine ultrafast electron diffuse scattering experiments and first-principles calculations of the coupled electron-phonon dynamics to provide a detailed momentum-resolved picture of lattice thermalization in black phosphorus. The measurements reveal the emergence of highly anisotropic nonthermal phonon populations persisting for several picoseconds after exciting the electrons with a light pulse. Ultrafast dynamics simulations based on the time-dependent Boltzmann formalism are supplemented by calculations of the structure factor, defining an approach to reproduce the experimental signatures of nonequilibrium structural dynamics. The combination of experiments and theory enables us to identify highly anisotropic electron-phonon scattering processes as the primary driving force of the nonequilibrium lattice dynamics in black phosphorus. Our approach paves the way toward unravelling and controlling microscopic energy flows in two-dimensional materials and van der Waals heterostructures, and may be extended to other nonequilibrium phenomena involving coupled electron-phonon dynamics such as superconductivity, phase transitions, or polaron physics.

While control over chemical reactions is largely achieved by altering the intrinsic properties of catalysts, novel strategies are constantly being proposed to improve the catalytic performance in an extrinsic way. Since the fundamental chemical behavior of molecules can remarkably change when their molecular scale is comparable to the size of the space where they are located, creating spatially confined environments around the active sites offers new means of regulating the catalytic processes. We demonstrate through first-principles calculations that acetylene hydrogenation can exhibit significantly improved selectivity within the confined sub-nanospace between two-dimensional (2D) monolayers and the Pd(111) substrate. Upon intercalation of molecules, the lifting and undulation of a 2D monolayer on Pd(111) influence the adsorption energies of intermediates to varying extents, which, in turn, changes the energy profiles of the hydrogenation reactions. Within the confined sub-nanospace, the formation of ethane is always unfavorable, demonstrating effective suppression of the unwanted overhydrogenation. Moreover, the catalytic properties can be further tuned by altering the coverage of the adsorbates as well as strains within the 2D monolayer. Our results also indicate that for improving the selectivity, the strategy of spatial confinement could not be combined with that of single-atom catalysis, since the reactant molecules cannot enter the sub-nanospace due to the too weak adsorbate-substrate interaction. This work sheds new light on designing novel catalysts with extraordinary performance for the selective hydrogenation of acetylene.

The LDA-1/2 method evaluates ionization potentials as the energy of the highest occupied molecular orbitals (HOMOs) at half occupation. It has proven to be a viable approach for calculating band gaps of semiconductors. To address its accuracy for finite systems, we apply LDA-1/2 to the atoms and molecules of the GW100 test set. The obtained HOMO energies are validated against CCSD(T) data and the G 0 W 0 approach of many-body perturbation theory. The accuracy of LDA-1/2 and G 0 W 0 is found to be the same, where the latter is computationally much more involved. To get insight into the benefits and limitations of the LDA-1/2 method, we analyze the impact of each assumption made in deriving the methodology.

In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3 ) hybrid inorganic-organic perovskite and its binary phase PbI 2 . The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. The theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.

In semiconductor quantum-wire heterostructures, interface roughness leads to exciton localization and to a radiative decay rate much smaller than that expected for structures with flat interfaces. Here, we uncover the electronic and optical properties of the one-dimensional extended defects that form at the intersection between stacking faults and inversion domain boundaries in GaN nanowires. We show that they act as crystal-phase quantum wires, a novel one-dimensional quantum system with atomically flat interfaces. These quantum wires efficiently capture excitons whose radiative decay gives rise to an optical doublet at 3.36 eV at 4.2 K. The binding energy of excitons confined in crystal-phase quantum wires is measured to be more than twice larger than that of the bulk. As a result of their unprecedented interface quality, these crystal-phase quantum wires constitute a model system for the study of one-dimensional excitons.

Hybrid organic-inorganic compounds attract a lot of interest for their flexible structures and multifunctional properties. For example, they can have coexisting magnetism and ferroelectricity whose possible coupling gives rise to magnetoelectricity. Here using first-principles computations, we show that, in a perovskite metal-organic framework (MOF), the magnetic and electric orders are further coupled to optical excitations, leading to an Electric tuning of the Magneto-Optical Kerr effect (EMOKE). Moreover, the Kerr angle can be switched by reversal of both ferroelectric and magnetic polarization only. The interplay between the Kerr angle and the organic-inorganic components of MOFs offers surprising unprecedented tools for engineering MOKE in complex compounds. Note that this work may be relevant to acentric magnetic systems in general, e.g., multiferroics.

Here we report a novel approach to synthesize atomically dispersed uniform clusters via a cage-separated precursor preselection and pyrolysis strategy. To illustrate this strategy, well-defined Ru 3 (CO) 12 was separated as a precursor by suitable molecular-scale cages of zeolitic imidazolate frameworks (ZIFs). After thermal treatment under confinement in the cages, uniform Ru 3 clusters stabilized by nitrogen species (Ru 3 /CN) were obtained. Importantly, we found that Ru 3 /CN exhibits excellent catalytic activity (100% conversion), high chemoselectivity (100% for 2-aminobenzaldehyde), and significantly high turnover frequency (TOF) for oxidation of 2-aminobenzyl alcohol. The TOF of Ru 3 /CN (4320 h -1 ) is about 23 times higher than that of small-sized (ca. 2.5 nm) Ru particles (TOF = 184 h -1 ). This striking difference is attributed to a disparity in the interaction between Ru species and adsorbed reactants.

By investigating the optoelectronic properties of prototypical graphene/hexagonal boron nitride (h-BN) heterostructures, we demonstrate how a nanostructured combination of these materials can lead to a dramatic enhancement of light-matter interaction and give rise to unique excitations. In the framework of ab initio many-body perturbation theory, we show that such heterostructures absorb light over a broad frequency range, from the near-infrared to the ultraviolet (UV), and that each spectral region is characterized by a specific type of excitations. Delocalized electron-hole pairs in graphene dominate the low-energy part of the spectrum, while strongly bound electron-hole pairs in h-BN are preserved in the near-UV. Besides these features, characteristic of the pristine constituents, charge-transfer excitations appear across the visible region. Remarkably, the spatial distribution of the electron and the hole can be selectively tuned by modulating the stacking arrangement of the individual building blocks. Our results open up unprecedented perspectives in view of designing van der Waals heterostructures with tailored optoelectronic features.

CONSPECTUS: Organic/inorganic hybrid structures are most exciting since one can expect new properties that are absent in either of their building blocks. They open new perspectives toward the design and tailoring of materials with desired features and functions. Prerequisite for real progress is, however, the in-depth understanding of what happens on the atomic and electronic scale. In this respect, hybrid materials pose a challenge for electronic-structure theory. Methods that proved useful for describing one side may not be applicable for the other one, and they are likely to fail for the interfaces. In this Account, we address the question to what extent we can quantitatively describe hybrid materials and where we even miss a qualitative description. We note that we are dealing with extended systems and thus adopt a solid-state approach. Therefore, density-functional theory (DFT) and many-body perturbation theory (MBPT), the GW approach for charged and the Bethe-Salpeter equation for neutral excitations, are our methods of choice. We give a brief summary of the used methodology, focusing on those aspects where problems can be expected when materials of different character meet at an interface. These issues are then taken up when discussing hybrid materials. We argue when and why, for example, standard DFT may fall short when it comes to the electronic structure of organic/metal interfaces or where the framework of MBPT can or must take over. Selected examples of organic/inorganic interfaces, structural properties, electronic bands, optical excitation spectra, and charge-transport properties as obtained from DFT and MBPT highlight which properties can be reliably computed for such materials. The crucial role of van der Waals forces is shown for sexiphenyl films, where the subtle interplay between intermolecular and molecule-substrate interactions is decisive for growth and morphologies. With a PTCDA monolayer on metal surfaces we discuss the performance of DFT in terms of interfacial electronic structure. We face the problem of a so far hidden variable, namely, electron-vibrational coupling, regarding level alignment at interfaces between organic and inorganic semiconductors. Poly(para-phenylene) adsorbed on graphene and encapsulated in carbon nanotubes represent case studies to demonstrate the impact of polarization effects and exciton delocalization in optoelectronic excitations, respectively. Polaron-induced band narrowing and its consequences for charge transport in organic crystals is exemplified for the HOMO bandwidth in naphthalene crystals. On the basis of these prototypical systems, we discuss what is missing to reach predictive power on a quantitative level for organic/inorganic hybrid materials and, thus, open a perspective toward the computational discovery of new materials for optoelectronic applications.

Nanopeapods, consisting of optically active π-conjugated molecules encapsulated inside of the cavity of carbon nanotubes, exhibit efficient photon emission in the visible spectral range. Combining optical experiments with ab initio theory, we show that the puzzling features observed in photoluminescence spectra are of excitonic nature. The subunits though being van der Waals bound are demonstrated to interact in the excited state, giving rise to the formation of hybrid excitons. We rationalize why this many-body effect makes such nanohybrids useful for optoelectronic devices.

Chemical-vapor-deposited large-area graphene is employed as the coating of transparent substrates for the growth of the prototypical organic n-type semiconductor perfluoropentacene (PFP). The graphene coating is found to cause face-on growth of PFP in a yet unknown substrate-mediated polymorph, which is solved by combining grazing-incidence X-ray diffraction with theoretical structure modeling. In contrast to the otherwise common herringbone arrangement of PFP in single crystals and "standing" films, we report a π-stacked arrangement of coplanar molecules in "flat-lying" films, which exhibit an exceedingly low π-stacking distance of only 3.07 Å, giving rise to significant electronic band dispersion along the π-stacking direction, as evidenced by ultraviolet photoelectron spectroscopy. Our study underlines the high potential of graphene for use as a transparent electrode in (opto-)electronic applications, where optimized vertical transport through flat-lying conjugated organic molecules is desired.

During the last years, self-assembled organic nanostructures have been recognized as a proper fundament for several electrical and optical applications. In particular, phenylenes deposited on muscovite mica have turned out to be an outstanding material combination. They tend to align parallel to each other forming needlelike structures. In that way, they provide the key for macroscopic highly polarized emission, waveguiding, and lasing. The resulting anisotropy has been interpreted so far by an induced dipole originating from the muscovite mica substrate. Based on a combined experimental and theoretical approach, we present an alternative growth model being able to explain molecular adsorption on sheet silicates in terms of molecule-surface interactions only. By a comprehensive comparison between experiments and simulations, we demonstrate that geometrical changes in the substrate surface or molecule lead to different molecular adsorption geometries and needle directions which can be predicted by our growth model.