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Many-body effects play an important role in enhancing and modifying optical absorption and other excited-state properties of solids in the perturbative regime, but their role in high harmonic generation (HHG) and other nonlinear response beyond the perturbative regime is not well-understood. We develop here an ab initio many-body method to study nonperturbative HHG based on the real-time propagation of the non-equilibrium Green’s function with the GW self energy. We calculate the HHG of monolayer MoS₂and obtain good agreement with experiment, including the reproduction of characteristic patterns of monotonic and nonmonotonic harmonic yield in the parallel and perpendicular responses, respectively. Here, we show that many-body effects are especially important to accurately reproduce the spectral features in the perpendicular response, which reflect a complex interplay of electron-hole interactions (or exciton effects) in tandem with the many-body renormalization and Berry curvature of the independent quasiparticle bandstructure.

 

In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

 

In the monolayer limit, 1⁢𝑇′ WTe2 is a two-dimensional topological insulator exhibiting the quantum spin Hall effect and is believed to host an excitonic insulator ground state. However, theoretical analysis of this system is complicated by the difficulty of obtaining descriptions of the single-quasiparticle band structure consistent with experimental measurement within conventional first-principles techniques. Previous band-structure calculations using the Perdew-Burke-Ernzerhof functional and a one-shot 𝐺⁢𝑊 approximation result in a semimetallic band structure, while calculations with hybrid functionals appear to open a band gap. Here, we demonstrate that self-consistently updating wave functions within a static 𝐺⁢𝑊 approximation (static COHSEX) can reproduce the insulating band structure experimentally observed by angle-resolved photoemission spectroscopy without resorting to mechanisms beyond the quasiparticle picture. Finally, a finite-momentum Bethe-Salpeter equation calculation on top of self-consistent 𝐺⁢𝑊 results in negative exciton excitation energies, leaving open the possibility of excitonic instability in 1⁢𝑇′ monolayer WTe2. 

Atomically thin two-dimensional transition-metal dichalcogenides (2D-TMDs) have emerged as semiconductors for next-generation nanoelectronics. As 2D-TMD-based devices typically utilize metals as the contacts, it is crucial to understand the properties of the 2D-TMD/metal interface, including the characteristics of the Schottky barriers formed at the semiconductor-metal junction. Conventional methods for investigating the Schottky barrier height (SBH) at these interfaces predominantly rely on contact-based electrical measurements with complex gating structures. In this study, we introduce an all-optical approach for non-contact measurement of the SBH, utilizing high-quality WS2/Au heterostructures as a model system. Our approach employs a below-bandgap pump to excite hot carriers from the gold into WS2 with varying thicknesses. By monitoring the resultant carrier density changes within the WS2 layers with a broadband probe, we traced the dynamics and magnitude of charge transfer across the interface. A systematic sweep of the pump wavelength enables us to determine the SBH values and unveil an inverse relationship between the SBH and the thickness of the WS2 layers. First-principles calculations reveal the correlation between the probability of injection and the density of states near the conduction band minimum of WS2. The versatile optical methodology for probing TMD/metal interfaces can shed light on the intricate charge transfer characteristics within various 2D heterostructures, facilitating the development of more efficient and scalable nano-electronic and optoelectronic technologies. 

We introduce a maximally localized Wannier function representation of Bloch excitons, two-particle correlated electron-hole excitations, in crystalline solids, where the excitons are maximally localized with respect to an average electron-hole coordinate in real space. As a proof-of-concept, we illustrate this representation in the case of low-energy spin-singlet and -triplet excitons in cubic lithium fluoride, computed using the ab initio Bethe-Salpeter equation approach. We visualize the resulting maximally localized exciton Wannier functions (MLXWFs) in real space, detail the convergence of the exciton Wannier spreads, and demonstrate how Wannier-Fourier interpolation can be leveraged to obtain exciton energies and states at arbitrary exciton crystal momenta in the Brillouin zone. We further introduce an approach to treat the long-range dipolar coupling between singlet MLXWFs and discuss it in depth. The MLXWF representation sheds light on the fundamental nature of excitons and paves the way toward Wannier-based post-processing of excitonic properties, enabling the construction of ab initio exciton tight-binding models, efficient interpolation of the exciton-phonon vertex, the computation of Berry curvature associated with exciton bands, and beyond. 

X-ray absorption spectroscopy (XAS) is a powerful experimental technique to probe the local order in materials with core electron excitations. Experimental interpretation requires supporting theoretical calculations. For water, these calculations are very demanding and, to date, could only be done with major approximations that limited the accuracy of the calculated spectra. This prompted an intense debate on whether a substantial revision of the standard picture of tetrahedrally bonded water was necessary to improve the agreement of theory and experiment. Here, we report a first-principles calculation of the XAS of water that avoids the approximations of prior work, thanks to recent advances in electron excitation theory. The calculated XAS spectra, and their variation with changes of temperature and/or with isotope substitution, are in good quantitative agreement with experiments. The approach requires accurate quasiparticle wave functions beyond density functional theory approximations, accounts for the dynamics of quasiparticles, and includes dynamic screening as well as renormalization effects due to the continuum of valence-level excitations. The three features observed in the experimental spectra are unambiguously attributed to excitonic effects. The preedge feature is associated with a bound intramolecular exciton, the main-edge feature is associated with an exciton localized within the coordination shell of the excited molecule, and the postedge feature is delocalized over more distant neighbors, as expected for a resonant state. The three features probe the local order at short, intermediate, and longer range relative to the excited molecule. The calculated spectra are fully consistent with a standard tetrahedral picture of water. 

Abstract Monolayer transition-metal dichalcogenides (TMDCs) show a wealth of exciton physics. Here, we report the existence of a new excitonic species, the high-lying exciton (HX), in single-layer WSe 2 with an energy of ~3.4 eV, almost twice the band-edge A-exciton energy, with a linewidth as narrow as 5.8 meV. The HX is populated through momentum-selective optical excitation in the K -valleys and is identified in upconverted photoluminescence (UPL) in the UV spectral region. Strong electron-phonon coupling results in a cascaded phonon progression with equidistant peaks in the luminescence spectrum, resolvable to ninth order. Ab initio GW -BSE calculations with full electron-hole correlations explain HX formation and unmask the admixture of upper conduction-band states to this complex many-body excitation. These calculations suggest that the HX is comprised of electrons of negative mass. The coincidence of such high-lying excitonic species at around twice the energy of band-edge excitons rationalizes the excitonic quantum-interference phenomenon recently discovered in optical second-harmonic generation (SHG) and explains the efficient Auger-like annihilation of band-edge excitons.