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We have used atomic layer-by-layer oxide molecular beam epitaxy to grow epitaxial thin films of La2-xCaxCuO4 with x up to 0.5, greatly exceeding the solubility limit of Ca in bulk systems (x~0.12). A comparison of the optical conductivity measured by spectroscopic ellipsometry to prior predictions from dynamical mean-field theory demonstrates that the hole concentration p is approximately equal to x. We find superconductivity with Tc of 15 to 20 K up to the highest doping levels and attribute the unusual stability of superconductivity in La2-xCaxCuO4 to the nearly identical radii of La and Ca ions, which minimizes the impact of structural disorder. We conclude that careful disorder management can greatly extend the "superconducting dome" in the phase diagram of the cuprates. [ABSTRACT FROM AUTHOR]

X‐ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure‐induced structural collapse in EuCo2P2. The spectral changes observed at the L3‐edge of Eu and K‐edges of Co and P suggest electron density redistribution, which contradicts the formal charges calculated from the commonly used Zintl–Klemm concept. Quantum‐chemical calculations show that, despite the increase in the oxidation state of Eu and the formation of a weak P−P bond in the high‐pressure phase, the electron transfer from the Eu 4f orbitals to the hybridized 5d and 6s states causes strengthening of the Eu−P and P−P bonds. These changes explain the increased electron density on P atoms, deduced from the P K‐edge XAS spectra. This work shows that the formal electron counting schemes do not provide an adequate description of changes associated with phase transitions in metallic systems with substantial mixing of the electronic states. [ABSTRACT FROM AUTHOR]

We have used atomic layer-by-layer oxide molecular beam epitaxy to grow epitaxial thin films of [Formula: see text] with x up to 0.5, greatly exceeding the solubility limit of Ca in bulk systems ([Formula: see text]). A comparison of the optical conductivity measured by spectroscopic ellipsometry to prior predictions from dynamical mean-field theory demonstrates that the hole concentration p is approximately equal to x. We find superconductivity with [Formula: see text] of 15 to 20 K up to the highest doping levels and attribute the unusual stability of superconductivity in [Formula: see text] to the nearly identical radii of La and Ca ions, which minimizes the impact of structural disorder. We conclude that careful disorder management can greatly extend the "superconducting dome" in the phase diagram of the cuprates., Competing Interests: The authors declare no competing interest., (Copyright © 2021 the Author(s). Published by PNAS.)

X-ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure-induced structural collapse in EuCo 2 P 2 . The spectral changes observed at the L 3 -edge of Eu and K-edges of Co and P suggest electron density redistribution, which contradicts the formal charges calculated from the commonly used Zintl-Klemm concept. Quantum-chemical calculations show that, despite the increase in the oxidation state of Eu and the formation of a weak P-P bond in the high-pressure phase, the electron transfer from the Eu 4f orbitals to the hybridized 5d and 6s states causes strengthening of the Eu-P and P-P bonds. These changes explain the increased electron density on P atoms, deduced from the P K-edge XAS spectra. This work shows that the formal electron counting schemes do not provide an adequate description of changes associated with phase transitions in metallic systems with substantial mixing of the electronic states., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)