Search for: All records

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.