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Abstract: We report on the electronic structure of doped LaFeO3 at the crossover from an insulating-to-metallic phase Transition. Comprehensive x-ray spectroscopic methodologies are used to understand core and valence electronic structure as well as crystal structure distortions associated with the electronic transition. Despite the antiferromagnetic (AFM) ordering at room temperature, we show direct evidence of itinerant carriers at the Fermi level revealed by resonant photoemission spectroscopy (RPES) at the Mo L3 edge. RPES data taken at the Fe L3 edge show spectral weight near the valence band edge and significant hybridization with O 2p states required for AFM ordering. Resonant inelastic x-ray scattering spectra taken across Fe L2, 3 edges show electron correlation effects (U) driven by Coulomb interactions of d electrons as well as broad charge-transfer excitations for x > 0.2 where the compound crosses over to a metallic state. Site substitution of Fe by Mo ions in the Fe-O6 octahedra enhances the separation of the two Fe-O bonds and Fe-O-Fe bonding angles relative to the orthorhombic LaFeO3, but no considerable Distortions are present to the overall structure. Mo ions appear to be homogeneously doped, with average valency of both metal sites monotonically decreasing with increasing Mo concentration. This insulator-to-metal phase transition with AFM stability is primarily understood through intermediate interaction strengths between correlation (U) and bandwidth (W) at the Fe site, where an estimation of this ratio is given. These results highlight the important role of extrinsic carriers in stabilizing a unique phase transition that can guide future efforts in antiferromagnetic-metal spintronics.

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Abstract: Utilising normal incidence X-ray standing waves we rigourously scrutinise the “inverted model” as the adsorption structure of free-base tetraphenyl porphyrin on Cu(111). We demonstrate that the iminic N atoms are anchored at near-bridge adsorption sites on the surface displaced laterally by 1.1 ± 0.2 Å in excellent agreement with previously published calculations.

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Abstract: A nearly free electron metal and a Mott insulating state can be thought of as opposite ends of the spectrum of possibilities for the motion of electrons in a solid. Understanding their interaction lies at the heart of the correlated electron problem. In the magnetic oxide metal PdCrO2, nearly free and Mott-localized electrons exist in alternating layers, forming natural heterostructures. Using angle-resolved photoemission spectroscopy, quantitatively supported by a strong coupling analysis, we show that the coupling between these layers leads to an “intertwined” excitation that is a convolution of the charge spectrum of the metallic layer and the spin susceptibility of the Mott layer. Our findings establish PdCrO2 as a model system in which to probe Kondo lattice physics and also open new routes to use the a priori nonmagnetic probe of photoemission to gain insights into the spin susceptibility of correlated electron materials.

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Abstract: The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.

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Abstract: Heteromolecular bilayers of π-conjugated organic molecules (COM) on metals, considered as model systems for more complex thin film heterostructures, are investigated with respect to their structural and electronic properties. By exploring the influence of the organic-metal interaction strength in bilayer systems, we determine the molecular arrangement in the physisorptive regime for copper-hexadecafluorophthalocyanine (F16CuPc) on Au(111) with intermediate layers of 5,7,12,14-pentacenetetrone (P4O) and perylene-3,4,9,10-tetracarboxylic diimide (PTCDI). Using the X-ray standing wave (XSW) technique to distinguish the different molecular layers, we show that these two bilayers are ordered following their deposition sequence. Surprisingly, F16CuPc as the second layer within the heterostructures exhibits an inverted intramolecular distortion compared to its monolayer structure.