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Point defect tolerance in materials, which extends operational lifetime, is essential for societal sustainability, and the creation of a framework to design such properties is a grand challenge in the material sciences. Using three prototypical lead bromide perovskites in single crystal form and high-resolution synchrotron-based X-ray spectroscopy, we reveal the unexpectedly pivotal role of the A-cation in mediating the influence of photoinduced defects. Organic A-cation hydrogen bonding facilitates chemical flexing of the lead-bromide bond that mitigates the self-doping effect of bromide vacancies. The contribution of partially ionic lead-bromide bonding to the electronic band edges, where the bonding becomes more ionic upon the formation of defects, mitigates re-hybridization of the electronic structure upon degradation. These findings reveal two new general design principles for defect tolerance in materials. Our findings uncover the foundations of defect tolerance in halide perovskites and have implications for defect calculations, all beam-based measurements of photophysical properties and perovskite solar cell technology.

We report on a combined experimental and theoretical study on CrI3 single crystals by employing the polarization dependence of resonant inelastic X-ray scattering (RIXS). Our investigations reveal multiple Cr 3d orbital splitting (dd excitations) as well as magnetic dichroism (MD) in the RIXS spectra which is evidence of spin-flip in the dd excitation. Interestingly, the dd excitation energies are similar on both sides of the ferromagnetic transition temperature, TC of 61 K, although MD in RIXS is predominant at 0.4 tesla magnetic field below TC. This demonstrates that the ferromagnetic superexchange interaction that is responsible for the intra-atomic exchange field, is vanishingly small compared to local exchange field that comes from exchange and correlation interaction among the interacting Cr 3d orbitals. The investigation presented here demonstrate that the electronic structure of bulk CrI3 is complex in the sense that dynamical electron correlations are significant. The recorded RIXS spectra reported here reveal clearly resolved Cr 3d intra-orbital dd excitations that represent transitions between electronic levels that are heavily influenced by multi-configuration effects. Our calculations employing the crystal field TTmultiplet theory taking into account the Cr 3d hybridization with the ligand valence states and the full multiplet structure due to intra-atomic and crystal field interactions in Oh and D3d symmetry, clearly reproduced the dichroic trend in experimental RIXS spectra., Comment: 7 pages, 4 figures

The nanoscience field often produces results more mystifying than any other discipline. It has been argued that changes in the plutonium dioxide (PuO2) particle size from bulk to nano can have a drastic effect on PuO2 properties. Here we report a full characterization of PuO2 nanoparticles (NPs) at the atomic level and probe their local and electronic structures by a variety of methods available at the synchrotron., Comment: Nanoscale (2020)

Fluorescence yield (FY) detected x-ray absorption spectra (XAS) of 3d transition metal ions are calculated from the integrated 2p3d resonant x-ray emission spectra. The resulting FY-XAS spectra are compared with the normal XAS spectra corresponding to the absorption cross section and significant deviations between the two spectra are found. This implies that the assumption that the FY-XAS spectrum identifies with the XAS spectrum is disproved. Especially for the early transition metal systems the differences between the FY-XAS and XAS are large, due to the opening of inelastic decay channels from selected x-ray absorption final states. The theoretical calculations show that the difference between FY detection and XAS is largest for the detection in depolarized geometry. The calculations are compared with experimental spectra for oxides and coordination compounds for Fe2+, Co2+ and Ni2+ systems. The implications for the sum rules in XAS and magnetic circular dichroism experiments are discussed.

The electronic structure of the heavy fermion compound CeB6 is probed by resonant inelastic soft X-ray scattering using photon energies across the Ce 3d and 4d absorption edges. The hybridization between the localized 4f orbitals and the delocalized valence-band states is studied by identifying the different spectral contributions from inelastic Raman scattering and normal fluorescence. Pronounced energy-loss structures are observed below the elastic peak at both the 3d and 4d thresholds. The origin and character of the inelastic scattering structures are discussed in terms of charge-transfer excitations in connection to the dipole allowed transitions with 4f character. Calculations within the single impurity Anderson model with full multiplet effects are found to yield consistent spectral functions to the experimental data., Comment: 9 pages, 4 figures, 1 table, http://link.aps.org/doi/10.1103/PhysRevB.63.075101

The electronic structure of CoO is studied by resonant inelastic soft X-ray scattering spectroscopy using photon energies across the Co 2p absorption edges. The different spectral contributions from the energy-loss structures are identified as Raman scattering due to d-d and charge-transfer excitations. For excitation energies close to the L3 resonance, the spectral features are dominated by quartet-quartet and quartet-doublet transitions of the 3d7 configuration. At excitation energies corresponding to the satellites in the Co 2p X-ray absorption spectrum of CoO, the emission features are instead dominated by charge-transfer transitions to the 3d8L-1 final state. The spectra are interpreted and discussed with the support of simulations within the single impurity Anderson model with full multiplet effects which are found to yield consistent spectral functions to the experimental data., Comment: 8 pages, 2 figures, 2 tables, http://link.aps.org/doi/10.1103/PhysRevB.65.205106