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In moir\'e crystals formed by stacking van der Waals (vdW) materials, surprisingly diverse correlated electronic phases and optical properties can be realized by a subtle change in the twist angle. Here, we discover that phonon spectra are also renormalized in MoS$_2$ twisted bilayers, adding a new perspective to moir\'e physics. Over a range of small twist angles, the phonon spectra evolve rapidly due to ultra-strong coupling between different phonon modes and atomic reconstructions of the moir\'e pattern. We develop a new low-energy continuum model for phonons that overcomes the outstanding challenge of calculating properties of large moir\'e supercells and successfully captures essential experimental observations. Remarkably, simple optical spectroscopy experiments can provide information on strain and lattice distortions in moir\'e crystals with nanometer-size supercells. The newly developed theory promotes a comprehensive and unified understanding of structural, optical, and electronic properties of moir\'e superlattices., Comment: 21 pages, 4 figures more...

The growing family of 2D materials led not long ago to combining different 2D layers and building artificial systems in the form of van der Waals heterostructures. Tailoring of heterostructure properties postgrowth would greatly benefit from a modification technique with a monolayer precision. However, appropriate techniques for material modification with this precision are still missing. To achieve such control, slow highly charged ions appear ideal as they carry high amounts of potential energy, which is released rapidly upon ion neutralization at the position of the ion. The resulting potential energy deposition is thus limited to just a few atomic layers (in contrast to the kinetic energy deposition). Here, we irradiated a freestanding van der Waals MoS2/graphene heterostructure with 1.3 keV/amu xenon ions in high charge states of 38, which led to nanometer-sized pores that appear only in the MoS2 facing the ion beam, but not in graphene beneath the hole. Reversing the stacking order leaves both layers undamaged, which we attribute to the high conductivity and carrier mobility in graphene acting as a shield for the MoS2 underneath. Our main focus is here on monolayer MoS2, but we also analyzed areas with few-layer structures and observed that the perforation is limited to the two topmost MoS2 layers, whereas deeper layers remain intact. Our results demonstrate that in addition to already being a valuable tool for materials processing, the usability of ion irradiation can be extended to mono- (or bi)layer manipulation of van der Waals heterostructures when the localized potential energy deposition of highly charged ions is also added to the toolbox. more...

Large deflections relevant for suspended circular graphene sheets with simply supported boundaries are computed by a theory for 2D membranes subjected to several types of vertical axisymmetric forc... more...

Band nesting occurs when conduction and valence bands are approximately equispaced over regions in the Brillouin zone. In two-dimensional materials, band nesting results in singularities of the joint density of states and thus in a strongly enhanced optical response at resonant frequencies. We exploit the high sensitivity of such resonances to small changes in the band structure to sensitively probe strain in semiconducting transition metal dichalcogenides (TMDs). We measure and calculate the polarization-resolved optical second harmonic generation (SHG) at the band nesting energies and present the first measurements of the energy-dependent nonlinear photoelastic effect in atomically thin TMDs (MoS2, MoSe2, WS2, and WSe2) combined with a theoretical analysis of the underlying processes. Experiment and theory are found to be in good qualitative agreement displaying a strong energy dependence of the SHG, which can be exploited to achieve exceptionally strong modulation of the SHG under strain. We attribute this sensitivity to a redistribution of the joint density of states for the optical response in the band nesting region. We predict that this exceptional strain sensitivity is a general property of all 2D materials with band nesting. more...

Funding Information: We acknowledge support from the FWF DACH project I3827-N36, COST action CA18234, the Academy of Finland through projects 316601 and 334532 and the doctoral colleges Solids4Fun W1243-N16 funded by the FWF and TU-D funded by TU Wien. Christoph Schattauer acknowledges support as a recipient of a DOC fellowship of the Austrian Academy of Sciences. Numerical calculations were performed on the Vienna Scientific Clusters VSC3 and VSC4. Funding Information: iPALM imaging was done in collaboration with the Advanced Imaging Center at Janelia Research Campus, a facility jointly supported by the Gordon and Betty Moore Foundation and the Howard Hughes Medical Institute. ChIA-Drop analysis was done by Minji Kim and Michał Denkiewicz. Molecular graphics and analyses performed with UCSF Chimera, developed by the Resource for Biocomputing, Visualization, and Informatics at the University of California, San Francisco, with support from NIH P41-GM103311. This work was carried out within „Three-dimensional Human Genome structure at the population scale: computational algorithm and experimental validation for lymphoblastoid cell lines of selected families from 1000 Genomes Project” project carried out within the TEAM programme of the Foundation for Polish Science co-financed by the European Union under the European Regional Development Fund, co-supported by Polish National Science Centre (2019/35/O/ST6/02484 and 2020/37/B/NZ2/03757) and the grant 1U54DK107967-01 “Nucleome Positioning System for Spatiotemporal Genome Organization and Regulation” within 4D Nucleome NIH program. The work was co-supported by the European Commission as Horizon 2020 Marie Skłodowska-Curie ITN Enhpathy grant “Molecular Basis of Human enhanceropathies”. DP was co-funded by Warsaw University of Technology within the Excellence Initiative: Research University (IDUB) programme; and POB Cybersecurity and data analysis of Warsaw University of Technology within the Excellence Initiative: Research University (IDUB) programme. Computations were performed thanks to the Laboratory of Bioinformatics and Computational Genomics, Faculty of Mathematics and Information Science, Warsaw University of Technology using Artificial Intelligence HPC platform financed by Polish Ministry of Science and Higher Education (decision no. 7054/IA/SP/2020 of 2020-08-28). Publisher Copyright: © 2022, The Author(s). We employ machine learning to derive tight-binding parametrizations for the electronic structure of defects. We test several machine learning methods that map the atomic and electronic structure of a defect onto a sparse tight-binding parameterization. Since Multi-layer perceptrons (i.e., feed-forward neural networks) perform best we adopt them for our further investigations. We demonstrate the accuracy of our parameterizations for a range of important electronic structure properties such as band structure, local density of states, transport and level spacing simulations for two common defects in single layer graphene. Our machine learning approach achieves results comparable to maximally localized Wannier functions (i.e., DFT accuracy) without prior knowledge about the electronic structure of the defects while also allowing for a reduced interaction range which substantially reduces calculation time. It is general and can be applied to a wide range of other materials, enabling accurate large-scale simulations of material properties in the presence of different defects. more...

Understanding the water splitting mechanism in photocatalysis is a rewarding goal as it will allow producing clean fuel for a sustainable life in the future. However, identifying the photocatalytic mechanisms by modeling photoactive nanoparticles requires sophisticated computational techniques based on multiscale modeling. In this review, we will survey the strengths and drawbacks of currently available theoretical methods at different length and accuracy scales. Understanding the surface-active site through Density Functional Theory (DFT) using new, more accurate exchange-correlation functionals plays a key role for surface engineering. Larger scale dynamics of the catalyst/electrolyte interface can be treated with Molecular Dynamics albeit there is a need for more generalizations of force fields. Monte Carlo and Continuum Modeling techniques are so far not the prominent path for modeling water splitting but interest is growing due to the lower computational cost and the feasibility to compare the modeling outcome directly to experimental data. The future challenges in modeling complex nano- photocatalysts involve combining different methods in a hierarchical way so that resources are spent wisely at each length scale, as well as accounting for excited states chemistry that is important for photocatalysis, a path that will bring devices closer to the theoretical limit of photocatalytic efficiency. more...

Transient absorption spectroscopy is a powerful tool to monitor the out-of-equilibrium optical response of photoexcited semiconductors. When this method is applied to two-dimensional semiconductors deposited on different substrates, the excited state optical properties are inferred from the pump-induced changes in the transmission/reflection of the probe, i.e., ΔT/T or ΔR/R. Transient optical spectra are often interpreted as the manifestation of the intrinsic optical response of the monolayer, including effects such as the reduction of the exciton oscillator strength, electron-phonon coupling or many-body interactions like bandgap renormalization, trion or biexciton formation. Here we scrutinize the assumption that one can determine the non-equilibrium optical response of the TMD without accounting for the substrate used in the experiment. We systematically investigate the effect of the substrate on the broadband transient optical response of monolayer MoS2 (1L-MoS2) by measuring ΔT/T and ΔR/R with different excitation photon energies. Employing the boundary conditions given by the Fresnel equations, we analyze the transient transmission/reflection spectra across the main excitonic resonances of 1L-MoS2. We show that pure interference effects induced by the different substrates explain the substantial differences (i.e., intensity, peak energy and exciton linewidth) observed in the transient spectra of the same monolayer. We thus demonstrate that the substrate strongly affects the magnitude of the exciton energy shift and the change of the oscillator strength in the transient optical spectra. By highlighting the key role played by the substrate, our results set the stage for a unified interpretation of the transient response of optoelectronic devices based on a broad class of TMDs. more...

Transient field-resolved spectroscopy enables studies of ultrafast dynamics in molecules, nanostructures, or solids with sub-cycle resolution, but previous work has so far concentrated on extracting the dielectric response at frequencies below 50\,THz. Here, we implemented transient field-resolved reflectometry at 50-100\,THz (3-6\,$\mu$m) with MHz repetition rate employing 800\,nm few-cycle excitation pulses that provide sub-10\,fs temporal resolution. The capabilities of the technique are demonstrated in studies of ultrafast photorefractive changes in the semiconductors Ge and GaAs, where the high frequency range permitted to explore the resonance-free Drude response. The extended frequency range in transient field-resolved spectroscopy can further enable studies with so far inaccessible transitions, including intramolecular vibrations in a large range of systems., Comment: 11 pages, 5 figures more...

Smoothly confined graphene quantum dots (GQDs) localize Dirac electrons with conserved spin and valley degrees of freedom. Recent experimental realization of such structures using a combination of magnetic fields and a scanning tunneling microscope tip showcased their potential in locally probing and adjusting the valley degree of freedom. The present work models the influence of lattice defects on the level structure of GQDs. We study both the adiabatic level spacing ``landscape''---orbital splitting and valley splitting---as well as transition dynamics between GQD states. The system is modeled using a tight-binding approach with on-site and hopping parameters in the vicinity of the defect region extracted from density functional theory via Wannier orbitals while time propagation is done using Magnus operators. Different defect types, such as double vacancy, Stone-Wales, flower, and Si substitution, are considered. We predict tunable valley splittings of the order of 2--20 meV. The level structure can thus be tailored at will by engineering appropriate defect geometries. more...

We construct a continuum model of twisted trilayer graphene using {\it ab initio} density-functional-theory calculations, and apply it to address twisted trilayer electronic structure. Our model accounts for moir\'e variation in site energies, hopping between outside layers and within layers. We focus on the role of a mirror symmetry present in ABA graphene trilayers with a middle layer twist. The mirror symmetry is lost intentionally when a displacement field is applied between layers, and unintentionally when the top layer is shifted laterally relative to the bottom layer. We use two band structure characteristics that are directly relevant to transport measurements, the Drude weight and the weak-field Hall conductivity, and relate them via the Hall density to assess the influence of the accidental lateral stacking shifts currently present in all experimental devices on electronic properties, and comment on the role of the possible importance of accidental lateral stacking shifts for superconductivity in twisted trilayers., Comment: 14 pages, 12 figures more...

Two-particle spectroscopy with correlated electron pairs is used to establish the causal link between the secondary electron spectrum, the $(\pi+\sigma)-$plasmon peak and the unoccupied band structure of highly oriented pyrolitic graphite. The plasmon spectrum is resolved with respect to the involved interband transitions and clearly exhibits final state effects, in particular due to the energy gap between the interlayer resonances along the $\Gamma$A-direction. The corresponding final state effects can also be identified in the secondary electron spectrum. Interpretation of the results is performed on the basis of density functional theory and tight binding calculations. Excitation of the plasmon perturbs the symmetry of the system and leads to hybridisation of the interlayer resonances with atom-like $\sigma^*$ bands along the $\Gamma A$-direction. These hybrid states have a high density of states as well as sufficient mobility along the graphite $c$-axis leading to the sharp $\sim$3\ eV resonance in the spectrum of emitted secondary electrons reported throughout the literature., Comment: 9 pages, 4 figures more...

In moiré crystals formed by stacking van der Waals materials, surprisingly diverse correlated electronic phases and optical properties can be realized by a subtle change in the twist angle. Here, we discover that phonon spectra are also renormalized in MoS more...

A gate-defined quantum dot in bilayer graphene is utilized as a sensitive electrometer for probing the charge density of its environment. Under the influence of a perpendicular magnetic field, the charge carrier density of the channel region next to the quantum dot oscillates due to the formation of Landau levels. This is experimentally observed as oscillations in the gate-voltage positions of the Coulomb resonances of the nearby quantum dot. From the frequency of the oscillations, we extract the charge carrier density in the channel and from the amplitude the shift of the quantum dot potential. We compare these experimental results with an electrostatic simulation of the device and find good agreement., Comment: 5 Pages, 4 Figures more...

We calculate the time evolution of the transient reflection signal in an MoS$_2$ monolayer on a SiO$_2$/Si substrate using first-principles out-of-equilibrium real-time methods. Our simulations provide a simple and intuitive physical picture for the delayed, yet ultrafast, evolution of the signal whose rise time depends on the excess energy of the pump laser: at laser energies above the A- and B-exciton, the pump pulse excites electrons and holes far away from the K valleys in the first Brillouin zone. Electron-phonon and hole-phonon scattering lead to a gradual relaxation of the carriers towards small $\textit{Active Excitonic Regions}$ around K, enhancing the dielectric screening. The accompanying time-dependent band gap renormalization dominates over Pauli blocking and the excitonic binding energy renormalization. This explains the delayed buildup of the transient reflection signal of the probe pulse, in excellent agreement with recent experimental data. Our results show that the observed delay is not a unique signature of an exciton formation process but rather caused by coordinated carrier dynamics and its influence on the screening. more...

Single-photon emitters play a key role in present and emerging quantum technologies. Several recent measurements have established monolayer ${\mathrm{WSe}}_{2}$ as a promising candidate for a reliable single-photon source. The origin and underlying microscopic processes have remained, however, largely elusive. We present a multiscale tight-binding simulation for the optical spectra of ${\mathrm{WSe}}_{2}$ under nonuniform strain and in the presence of point defects employing the Bethe-Salpeter equation. Strain locally shifts excitonic energy levels into the band gap where they overlap with localized intragap defect states. The resulting hybridization allows for efficient filling and subsequent radiative decay of the defect states. We identify intervalley defect excitonic states as the likely candidate for antibunched single-photon emission. This proposed scenario is shown to account for a large variety of experimental observations including brightness, radiative transition rates, the variation of the excitonic energy with applied magnetic and electric fields as well as the variation of the polarization of the emitted photon with the magnetic field. more...

Embedding theories offer an elegant solution to overcome intrinsic algorithmic scaling and accuracy limitations of simulation methods. These theories also promise to achieve the accuracy of high-level electronic structure techniques at near the computational cost of much less accurate levels of theory by exploiting positive traits of multiple methods. Of crucial importance to fulfilling this promise is the ability to combine diverse theories in an embedding simulation. However, these methods may utilize different basis set and electron-ion potential representations. In this first part of a two-part account of implementing potential functional embedding theory (PFET) at a correlated wave function level, we discuss remedies to basis set and electron-ion potential discrepancies and assess the performance of the PFET scheme with mixed basis sets. more...

We investigate transport through nanoribbons in the presence of disorder scattering. We show that size quantization patterns are only present when SU(2) pseudospin symmetry is preserved. Symmetry breaking disorder renders transverse quantization invisible, which may provide an explanation for the necessity of suspending graphene nanoconstrictions to obtain size quantization signatures in very recent experiments. Employing a quasi-classical Monte-Carlo simulation, we are able to reproduce and explain key qualitative features of the full quantum-mechanical calculations. more...

We present an embedding approach to treat local electron correlation effects in periodic environments. In a single, consistent framework, our plane-wave based scheme embeds a local high-level correlation calculation (here Coupled Cluster Theory, CC), employing localized orbitals, into a low-level correlation calculation (here the direct Random Phase Approximation, RPA). This choice allows for an accurate and effcient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersion are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite, for instance, is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons., 6 pages, 2 figures more...

Profound investigation of the unsurpassed mechanical properties of suspended graphene motivates the link between classical continuum mechanics (where the notions of “mechanical strength”, “mechanical stiffness”, and “elastic energy” have actually been coined) and density functional theory (DFT) rooted in quantum mechanics. Namely, the latter quantifies the energetic ground states of systems consisting of atomic nuclei and electrons; and these ground states, in turn, are directly linked to the elastic energy. While the corresponding state-of-the-art typically concerns graphene mechanics under uniaxial or equally biaxial strain states, we here present a fully anisotropic free (strain) energy function reflecting DFT-simulations associated with tens of thousands of arbitrary biaxial strain states. The latter are realized as sets of primitive unit cell vectors spanning a rhomboid unit cell hosting two carbon atoms. The position of the latter follows from internal energy minimization through the Vienna ab initio simulation package (VASP). As corresponding continuum mechanical representation we employ hyperelastic, structure tensor-based polynomial models up to the fifth order. The corresponding stress-strain relations are of concave nature, and hence, they provide access to the failure limits of the 2D material undergoing arbitrary loading situations. This is expected to introduce a new level of precision in the growing field of the structural mechanics of graphene. more...

Owing to its low excitation energy and long radiative lifetime, the first excited isomeric state of thorium-229

The first nuclear excited state of $^{229}$Th offers the unique opportunity for laser-based optical control of a nucleus. Its exceptional properties allow for the development of a nuclear optical clock which offers a complementary technology and is expected to outperform current electronic-shell based atomic clocks. The development of a nuclear clock was so far impeded by an imprecise knowledge of the energy of the $^{229}$Th nuclear excited state. In this letter we report a direct excitation energy measurement of this elusive state and constrain this to 8.28$\pm$0.17 eV. The energy is determined by spectroscopy of the internal conversion electrons emitted in-flight during the decay of the excited nucleus in neutral $^{229}$Th atoms. The nuclear excitation energy is measured via the valence electronic shell, thereby merging the fields of nuclear- and atomic physics to advance precision metrology. The transition energy between ground and excited state corresponds to a wavelength of 149.7$\pm$3.1 nm. These findings set the starting point for high-resolution nuclear laser spectroscopy and thus the development of a nuclear optical clock of unprecedented accuracy. A nuclear clock is expected to have a large variety of applications, ranging from relativistic geodesy over dark matter research to the observation of potential temporal variation of fundamental constants. more...

We report on measurements of quantized conductance in gate-defined quantum point contacts in bilayer graphene that allow the observation of subband splittings due to spin-orbit coupling. The size of this splitting can be tuned from 40 to 80 $\mu$eV by the displacement field. We assign this gate-tunable subband-splitting to a gap induced by spin-orbit coupling of Kane-Mele type, enhanced by proximity effects due to the substrate. We show that this spin-orbit coupling gives rise to a complex pattern in low perpendicular magnetic fields, increasing the Zeeman splitting in one valley and suppressing it in the other one. In addition, we observe the existence of a spin-polarized channel of 6 e$^2$/h at high in-plane magnetic field and of signatures of interaction effects at the crossings of spin-split subbands of opposite spins at finite magnetic field., Comment: 5 pages, 4 figures, Supplement 6 figures more...

We demonstrate that multi-photon photoemission including above-threshold multiphoton orders from a nanotip can be coherently controlled with the optical phase between two light fields. By focusing 74 fs drive pulses at 1560 nm and their second harmonic at 780 nm onto the tip and changing the optical phase between the two colors, we observe an emission current modulation of up to 97.5 %. Additionally, electron energy spectra reveal a homogeneous modulation of all multiphoton orders. Hence, the electron current can be strongly increased (by a factor of 3.7) or almost completely turned off due to interference between two different quantum channels in the material. We argue that the extremely high degree of coherence evidenced by this near-unity current modulation depth is due to the confinement of the local field enhancement at the nanotip. The nano-rod effect allows to apply large DC fields, adding a further degree of freedom to investigate the modulation contrast of the photoemitted electron yield. We show that for an increasing DC electric field a non-cooperative distribution of electron emission leads to a decrease in modulation contrast. more...

We present measurements of quantized conductance in electrostatically induced quantum point contacts in bilayer graphene. The application of a perpendicular magnetic field leads to an intricate pattern of lifted and restored degeneracies with increasing field: at zero magnetic field the degeneracy of quantized one-dimensional subbands is four, because of a twofold spin and a twofold valley degeneracy. By switching on the magnetic field, the valley degeneracy is lifted. Because of the Berry curvature, states from different valleys split linearly in magnetic field. In the quantum Hall regime fourfold degenerate conductance plateaus reemerge. During the adiabatic transition to the quantum Hall regime, levels from one valley shift by two in quantum number with respect to the other valley, forming an interweaving pattern that can be reproduced by numerical calculations., We acknowledge financial support from the European Graphene Flagship, the Swiss National Science Foundation via NCCR Quantum Science and Technology, ERC Synergy Hetero 2D, WWTF Project No. MA14-002, and MECD. Calculations were performed on the Vienna Scientific Cluster (VSC). Growth of hexagonal boron nitride crystals was supported by the Elemental Strategy Initiative conducted by MEXT, Japan and the CREST (JPMJCR15F3), JST, EC Project 2D·SIPC, Grant No. 820378. more...

We present magneto-Raman spectroscopy measurements on suspended graphene to investigate the charge carrier density-dependent electron-electron interaction in the presence of Landau levels. Utilizing gate-tunable magneto-phonon resonances, we extract the charge carrier density dependence of the Landau level transition energies and the associated effective Fermi velocity $v_\mathrm{F}$. In contrast to the logarithmic divergence of $v_\mathrm{F}$ at zero magnetic field, we find a piecewise linear scaling of $v_\mathrm{F}$ as a function of charge carrier density, due to a magnetic field-induced suppression of the long-range Coulomb interaction. We quantitatively confirm our experimental findings by performing tight-binding calculations on the level of the Hartree-Fock approximation, which also allow us to estimate an excitonic binding energy of $\approx$ 6 meV contained in the experimentally extracted Landau level transitions energies., Comment: 10 pages, 6 figures more...

The interaction between O2 molecules and Al surfaces has long been poorly understood despite its importance in diverse chemical phenomena. Early experimental investigations of adsorption dynamics indicated that abstraction of a single O atom by the surface, instead of dissociative chemisorption, dominates at low O2 incident kinetic energies. Abstraction of the closer O atom suggests low barrier heights at perpendicular incidence. However, recent measurements suggest that parallel O2 orientations dominate sticking at low energies. We resolve this apparent contradiction by a systematic ab initio embedded correlated wavefunction study of the stereochemistry of O2 reacting with Al(111). We identify two important new details: (i) initially, roughly parallel oxygen molecules tend to tilt upright while approaching the surface, suggesting that the abstraction channel does dominate at low energies and (ii) the reaction channel with the lowest barrier indeed corresponds to a parallel orientation, which ultimately evolves either into dissociative chemisorption or toward abstraction. more...

We present an approach for embedding defect structures modeled by density functional theory into large-scale tight-binding simulations. We extract local tight-binding parameters for the vicinity of the defect site using Wannier functions. In the transition region between the bulk lattice and the defect the tight-binding parameters are continuously adjusted to approach the bulk limit far away from the defect. This embedding approach allows for an accurate high-level treatment of the defect orbitals using as many as ten nearest neighbors while keeping a small number of nearest neighbors in the bulk to render the overall computational cost reasonable. As an example of our approach, we consider an extended graphene lattice decorated with Stone-Wales defects, flower defects, double vacancies, or silicon substitutes. We predict distinct scattering patterns mirroring the defect symmetries and magnitude that should be experimentally accessible. more...

We present density functional embedding for diffusion Monte Carlo calculations (DMC). Using two test systems, an H chain and a Be slab, we demonstrate the feasibility and show that the approach can give high-quality results. DMC embedded in potentials from density functional embedding theory thus presents an alternative to conventional embedded quantum chemical methods, such as embedded complete active space calculations. This is especially true for cases in which the cluster size becomes too large for accurate wave-function theory based methods or for cases in which basis-set superposition errors become dominant. Furthermore, we show that embedded DMC can easily be used for systems in which the cluster of interest is a one-dimensional or two-dimensional periodic object and cannot be described as isolated impurity. This extends the applicability of the embedding approach to new fields. more...

Synopsis We demonstrate coherently controlled two-color above-threshold photoemission from a single crystal tungsten nanotip. With optimized fundamental and second harmonic intensities near perfect phase contrast can be obtained. more...

Conspectus Ab initio modeling of matter has become a pillar of chemical research: with ever-increasing computational power, simulations can be used to accurately predict, for example, chemical reaction rates, electronic and mechanical properties of materials, and dynamical properties of liquids. Many competing quantum mechanical methods have been developed over the years that vary in computational cost, accuracy, and scalability: density functional theory (DFT), the workhorse of solid-state electronic structure calculations, features a good compromise between accuracy and speed. However, approximate exchange-correlation functionals limit DFT's ability to treat certain phenomena or states of matter, such as charge-transfer processes or strongly correlated materials. Furthermore, conventional DFT is purely a ground-state theory: electronic excitations are beyond its scope. Excitations in molecules are routinely calculated using time-dependent DFT linear response; however applications to condensed matter are still limited. By contrast, many-electron wavefunction methods aim for a very accurate treatment of electronic exchange and correlation. Unfortunately, the associated computational cost renders treatment of more than a handful of heavy atoms challenging. On the other side of the accuracy spectrum, parametrized approaches like tight-binding can treat millions of atoms. In view of the different (dis-)advantages of each method, the simulation of complex systems seems to force a compromise: one is limited to the most accurate method that can still handle the problem size. For many interesting problems, however, compromise proves insufficient. A possible solution is to break up the system into manageable subsystems that may be treated by different computational methods. The interaction between subsystems may be handled by an embedding formalism. In this Account, we review embedded correlated wavefunction (CW) approaches and some applications. We first discuss our density functional embedding theory, which is formally exact. We show how to determine the embedding potential, which replaces the interaction between subsystems, at the DFT level. CW calculations are performed using a fixed embedding potential, that is, a non-self-consistent embedding scheme. We demonstrate this embedding theory for two challenging electron transfer phenomena: (1) initial oxidation of an aluminum surface and (2) hot-electron-mediated dissociation of hydrogen molecules on a gold surface. In both cases, the interaction between gas molecules and metal surfaces were treated by sophisticated CW techniques, with the remainder of the extended metal surface being treated by DFT. Our embedding approach overcomes the limitations of conventional Kohn-Sham DFT in describing charge transfer, multiconfigurational character, and excited states. From these embedding simulations, we gained important insights into fundamental processes that are crucial aspects of fuel cell catalysis (i.e., O2 reduction at metal surfaces) and plasmon-mediated photocatalysis by metal nanoparticles. Moreover, our findings agree very well with experimental observations, while offering new views into the chemistry. We finally discuss our recently formulated potential-functional embedding theory that provides a seamless, first-principles way to include back-action onto the environment from the embedded region. more...

We present an embedding approach for semiconductors and insulators based on or- bital rotations in the space of occupied Kohn-Sham orbitals. We have implemented our approach in the popular VASP software package. We demonstrate its power for defect structures in silicon and polaron formation in titania, two challenging cases for conventional Kohn-Sham density functional theory., 2 figures more...

We numerically examine the high-harmonic generation in graphene caused by an intense few-cycle terahertz laser field by solving the time-dependent Dirac equation. The observed spectra feature a complex interplay of interband and intraband electron dynamics. At high harmonic frequencies, we observe a plateau region with a cut-off frequency linearly proportional to the laser field. The linear dependence of the cutoff on the field resembles the behavior for electrons driven in bulk crystals but differs from the case of atoms or molecules. The unique features of the graphene band structure allow for a transparent decomposition of interband and intraband contributions and for an analytic estimate of the harmonic cut-off frequency in excellent agreement with the simulations. more...

Quantum mechanical embedding theories partition a complex system into multiple spatial regions that can use different electronic structure methods within each, to optimize trade-offs between accuracy and cost. The present work incorporates accurate but expensive correlated wave function (CW) methods for a subsystem containing the phenomenon or feature of greatest interest, while self-consistently capturing quantum effects of the surroundings using fast but less accurate density functional theory (DFT) approximations. We recently proposed two embedding methods [for a review, see: Acc. Chem. Res. 2014 , 47 , 2768 ]: density functional embedding theory (DFET) and potential functional embedding theory (PFET). DFET provides a fast but non-self-consistent density-based embedding scheme, whereas PFET offers a more rigorous theoretical framework to perform fully self-consistent, variational CW/DFT calculations [as defined in part 1, CW/DFT means subsystem 1(2) is treated with CW(DFT) methods]. When originally presented, PFET was only tested at the DFT/DFT level of theory as a proof of principle within a planewave (PW) basis. Part 1 of this two-part series demonstrated that PFET can be made to work well with mixed Gaussian type orbital (GTO)/PW bases, as long as optimized GTO bases and consistent electron-ion potentials are employed throughout. Here in part 2 we conduct the first PFET calculations at the CW/DFT level and compare them to DFET and full CW benchmarks. We test the performance of PFET at the CW/DFT level for a variety of types of interactions (hydrogen bonding, metallic, and ionic). By introducing an intermediate CW/DFT embedding scheme denoted DFET/PFET, we show how PFET remedies different types of errors in DFET, serving as a more robust type of embedding theory. more...

Since the first experimental realizations of graphene nanoribbons,1 graphene nanodevices2 have attracted enormous attention in the quest for future nanoscale technologies. Because of their small band gaps and high charge-carrier mobilities, n-acenes (Figure ​(Figure1)1) and functionalized acenes are being considered as highly interesting building units for organic electronic materials.3 Zigzag nanoribbons feature remarkable spin-polarization and half-metallic properties4 and chemically fascinating challenges have to be solved in the synthesis of such extended polyaromatic hydrocarbons (PAHs).5 Moreover, the chemical properties of graphene nanoribbons may be linked to the reactivity of black carbon surfaces and PAHs in soils, affecting the accumulation of persistent organic pollutants with environmental implications.6 more...

Physical systems with loss or gain have resonant modes that decay or grow exponentially with time. Whenever two such modes coalesce both in their resonant frequency and their rate of decay or growth, an 'exceptional point' occurs, giving rise to fascinating phenomena that defy our physical intuition. Particularly intriguing behaviour is predicted to appear when an exceptional point is encircled sufficiently slowly, such as a state-flip or the accumulation of a geometric phase. The topological structure of exceptional points has been experimentally explored, but a full dynamical encircling of such a point and the associated breakdown of adiabaticity have remained out of reach of measurement. Here we demonstrate that a dynamical encircling of an exceptional point is analogous to the scattering through a two-mode waveguide with suitably designed boundaries and losses. We present experimental results from a corresponding waveguide structure that steers incoming waves around an exceptional point during the transmission process. In this way, mode transitions are induced that transform this device into a robust and asymmetric switch between different waveguide modes. This work will enable the exploration of exceptional point physics in system control and state transfer schemes at the crossroads between fundamental research and practical applications. more...

The nonlinear response of graphene to a THz laser pulse is studied by solving the time-dependent Dirac equation and the time-dependent Schr\"odinger equation within a tight-binding approximation applied to finite-sized structures. We compare predictions of these two approximations for the harmonic spectrum with the recent experiment by P. Bowlan et al. [Phys. Rev. B 89, 041408(R) (2014)]. We highlight the influence of short-range and long-range disorder which can be accounted for within the tight-binding description on a microscopic level. We find good agreement with the experiment. Most notably, the intensity of the second harmonic offers a quantitative indicator for the amount of short-range disorder. more...

Quantum point contacts (QPCs) are cornerstones of mesoscopic physics and central building blocks for quantum electronics. Although the Fermi wave-length in high-quality bulk graphene can be tuned up to hundreds of nanometers, the observation of quantum confinement of Dirac electrons in nanostructured graphene systems has proven surprisingly challenging. Here we show ballistic transport and quantized conductance of size-confined Dirac fermions in lithographically-defined graphene constrictions. At high charge carrier densities, the observed conductance agrees excellently with the Landauer theory of ballistic transport without any adjustable parameter. Experimental data and simulations for the evolution of the conductance with magnetic field unambiguously confirm the identification of size quantization in the constriction. Close to the charge neutrality point, bias voltage spectroscopy reveals a renormalized Fermi velocity ($v_F \approx 1.5 \times 10^6 m/s$) in our graphene constrictions. Moreover, at low carrier density transport measurements allow probing the density of localized states at edges, thus offering a unique handle on edge physics in graphene devices., 24 pages including 20 figures and 1 table. Corrected typos. To appear in Nature Communications more...

We investigate transport through bulk-disordered graphene nanoribbons and nanoconstrictions. Employing a modular recursive Green’s function algorithm, we study devices of realistic size (up to 100.000 nm). By Fourier transforming the scattered wave we disentangle inter-valley scattering between the two Dirac cones of graphene and intra-valley scattering on a single cone. We find that different types of defects leave characteristic signatures on transport properties which we can describe with a simplified scattering model. A quantitative comparison with recent experimental data is performed which yields insights into the disorder concentration in realistic samples. more...

We demonstrate coherent control of multiphoton and above-threshold photoemission from a single solid-state nanoemitter driven by a fundamental and a weak second harmonic laser pulse. Depending on the relative phase of the two pulses, electron emission is modulated with a contrast of the oscillating current signal of up to 94%. Electron spectra reveal that all observed photon orders are affected simultaneously and similarly. We confirm that photoemission takes place within 10 fs. Accompanying simulations indicate that the current modulation with its large contrast results from two interfering quantum pathways leading to electron emission., 12 pages, 4 figures more...

We study wave functions and their nodal patterns in Andreev billiards consisting of a normal-conducting (N) ballistic quantum dot in contact with a superconductor (S). The bound states in such systems feature an electron and a hole component which are coherently coupled by the scattering of electrons into holes at the S-N interface. The wave function “lives” therefore on two sheets of configuration space, each of which features, in general, distinct nodal patterns. By comparing the wave functions and their nodal patterns for holes and electrons detailed tests of semiclassical predictions become possible. One semiclassical theory based on ideal Andreev retroreflection predicts the electron- and hole eigenstates to perfectly mirror each other. We probe the limitations of validity of this model both in terms of the spectral density of the eigenstates and the shape of the wavefunctions in the electron and hole sheet. We identify cases where the Chladni figures for the electrons and holes drastically differ from each other and explain these discrepancies by limitations of the retroreflection picture. more...

We report a new implementation of the density functional embedding theory (DFET) in the VASP code, using the projector-augmented-wave (PAW) formalism. Newly developed algorithms allow us to efficiently perform optimized effective potential optimizations within PAW. The new algorithm generates robust and physically correct embedding potentials, as we verified using several test systems including a covalently bound molecule, a metal surface, and bulk semiconductors. We show that with the resulting embedding potential, embedded cluster models can reproduce the electronic structure of point defects in bulk semiconductors, thereby demonstrating the validity of DFET in semiconductors for the first time. Compared to our previous version, the new implementation of DFET within VASP affords use of all features of VASP (e.g., a systematic PAW library, a wide selection of functionals, a more flexible choice of U correction formalisms, and faster computational speed) with DFET. Furthermore, our results are fairly robust with respect to both plane-wave and Gaussian type orbital basis sets in the embedded cluster calculations. This suggests that the density functional embedding method is potentially an accurate and efficient way to study properties of isolated defects in semiconductors. more...

Magneto-optical transitions between Landau levels can provide precise spectroscopic information on the electronic structure and excitation spectra of graphene, enabling probes of substrate and many-body effects. We calculate the magneto-optical conductivity of large-size graphene flakes using a tight-binding approach. Our method allows us to directly compare the magneto-optical response of an isolated graphene flake with one aligned on hexagonal boron nitride giving rise to a periodic superlattice potential. The substrate interaction induces band gaps away from the Dirac point. In the presence of a perpendicular magnetic field Landau-level like structures emerge from these zero-field band gaps. The energy dependence of these satellite structures is, however, not easily accessible by conventional probes of the density of states by varying the back-gate voltage. Here we propose the magneto-optical probing of the superlattice perturbed spectrum. Our simulation includes magneto-excitonic effects in first-order perturbation theory. Our approach yields a quantitative explanation of recently observed Landau-level dependent renormalizations of the Fermi velocity., 8 pages, 3 figures more...