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Register a new userReal time cumulant approach for charge transfer satellites in x-ray photoemission spectra
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X-ray photoemission spectra generally exhibit satellite features in addition to the quasi-particle peaks due to many-body excitations, which have been of considerable theoretical and experimental interest. However, the satellites attributed to charge-transfer (CT) excitations in correlated materials have proved difficult to calculate from first principles. Here we report a real-time, real-space approach for such calculations based on a cumulant representation of the core-hole Greens function and time-dependent density functional theory. This approach also yields an interpretation of CT satellites in terms of a complex oscillatory, transient response to a suddenly created core hole. Illustrative results for TiO$_2$ and NiO are in good agreement with experiment.
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Inelastic losses in core level x-ray spectra arise from many-body excitations, leading to broadening and damping as well as satellite peaks in x-ray photoemission (XPS) and x-ray absorption (XAS) spectra. Here we present a practical approach for calculating these losses based on a cumulant representation of the particle-hole Greens function, a quasi-boson approximation, and a partition of the cumulant into extrinsic, intrinsic and interference terms. The intrinsic losses are calculated using real-time, time-dependent density functional theory while the extrinsic losses are obtained from the GW approximation of the photo-electron self-energy and the interference terms are approximated. These effects are included in the spectra using a convolution with an energy dependent particle-hole spectral function. The approach elucidates the nature of the spectral functions in XPS and XAS and explains the significant cancellation between extrinsic and intrinsic losses. Edge-singularity effects in metals are also accounted for. Illustrative results are presented for the XPS and XAS for both weakly and more correlated systems.
Luminescence spectra of NiO have been investigated under vacuum ultraviolet (VUV) and soft X-ray (XUV) excitation. Photoluminescence (PL) spectra show broad emission bands centered at about 2.3 and 3.2 eV. The PL excitation (PLE) spectral evolution and lifetime measurements reveal that two mechanisms with short and long decay times, attributed to the d($e_g$)-d($e_g$) and p($pi$)-d charge transfer (CT) transitions in the range 4-6,eV, respectively, are responsible for the observed emissions, while the most intensive p($sigma$)-d CT transition at 7,eV appears to be a weak if any PL excitation mechanism. The PLE spectra recorded in the 4-7,eV range agree with the RIXS and reflectance data. Making use of the XUV excitation allows us to avoid the predominant role of the surface effects in luminescence and reveal bulk luminescence with puzzling well isolated doublet of very narrow lines with close energies near 3.3,eV characteristic for recombination transitions in self-trapped emph{d}-emph{d} CT excitons formed by coupled Jahn-Teller Ni$^+$ and Ni$^{3+}$ centers. This conclusion is supported both by a comparative analysis of the luminescence spectra for NiO and solid solutions Ni$_{x}$Zn$_{1-x}$O, and by a comprehensive cluster model assignement of different emph{p}-emph{d} and emph{d}-emph{d} CT transitions, their relaxation channels. To the best of our knowledge it is the first observation of the self-trapping for emph{d}-emph{d} CT excitons. Our paper shows the time resolved luminescence measurements provide an instructive tool for elucidation of the emph{p}-emph{d} and emph{d}-emph{d} CT excitations and their relaxation in 3d oxides.
By using laboratory x-ray photoemission spectroscopy (XPS) and hard x-ray photoemission spectroscopy (HX-PES) at a synchrotron facility, we report an empirical semi-quantitative relationship between the valence/core-level x-ray photoemission spectral weight and electrical conductivity in La_{1-x}Sr_{x}MnO_{3} as a function of x. In the Mn 2p_{3/2} HX-PES spectra, we observed the shoulder structure due to the Mn^{3+} well-screened state. However, the intensity at x=0.8 was too small to explain its higher electrical conductivity than x=0.0, which confirms our recent analysis on the Mn 2p_{3/2} XPS spectra. The near-Fermi level XPS spectral weight was found to be a measure of the variation of electrical conductivity with x in spite of a far lower energy resolution compared with the energy scale of the quasiparticle (coherent) peak because of the concurrent change of the coherent and incoherent spectral weight.
Motivated by recent experimental suggestions of charge-order-driven ferroelectricity in organic charge-transfer salts, such as $kappa$-(BEDT-TTF)$_2$Cu[N(CN)$_2$]Cl, we investigate magnetic and charge-ordered phases that emerge in an extended two-orbital Hubbard model on the anisotropic triangular lattice at $3/4$ filling. This model takes into account the presence of two organic BEDT-TTF molecules, which form a dimer on each site of the lattice, and includes short-range intramolecular and intermolecular interactions and hoppings. By using variational wave functions and quantum Monte Carlo techniques, we find two polar states with charge disproportionation inside the dimer, hinting to ferroelectricity. These charge-ordered insulating phases are stabilized in the strongly correlated limit and their actual charge pattern is determined by the relative strength of intradimer to interdimer couplings. Our results suggest that ferroelectricity is not driven by magnetism, since these polar phases can be stabilized also without antiferromagnetic order and provide a possible microscopic explanation of the experimental observations. In addition, a conventional dimer-Mott state (with uniform density and antiferromagnetic order) and a nonpolar charge-ordered state (with charge-rich and charge-poor dimers forming a checkerboard pattern) can be stabilized in the strong-coupling regime. Finally, when electron-electron interactions are weak, metallic states appear, with either uniform charge distribution or a peculiar $12$-site periodicity that generates honeycomb-like charge order.
Charge order is universal among high-T$_c$ cuprates but its relevance to superconductivity is not established. It is widely believed that, while static order competes with superconductivity, dynamic order may be favorable and even contribute to Cooper pairing. We use time-resolved resonant soft x-ray scattering to study the collective dynamics of the charge order in the prototypical cuprate, La$_{2-x}$Ba$_x$CuO$_4$. We find that, at energy scales $0.4$ meV $ lesssim omega lesssim 2$ meV, the excitations are overdamped and propagate via Brownian-like diffusion. At energy scales below 0.4 meV the charge order exhibits dynamic critical scaling, displaying universal behavior arising from propagation of topological defects. Our study implies that charge order is dynamic, so may participate tangibly in superconductivity.
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