Kondo-Induced Giant Isotropic Negative Thermal Expansion.

Negative thermal expansion is an unusual phenomenon appearing in only a handful of materials, but pursuit and mastery of the phenomenon holds great promise for applications across disciplines and industries. Here we report use of x-ray spectroscopy and diffraction to investigate the 4f-electronic properties in Y-doped SmS and employ the Kondo volume collapse model to interpret the results. Our measurements reveal an unparalleled decrease of the bulk Sm valence by over 20% at low temperatures in the mixed-valent golden phase, which we show is caused by a strong coupling between an emergent Kondo lattice state and a large isotropic volume change. The amplitude and temperature range of the negative thermal expansion appear strongly dependent on the Y concentration and the associated chemical disorder, providing control over the observed effect. This finding opens avenues for the design of Kondo lattice materials with tunable, giant, and isotropic negative thermal expansion.

Kondo interactions from band reconstruction in YbInCu(4).

We combine resonant inelastic x-ray scattering and model calculations in the Kondo lattice compound YbInCu_{4}, a system characterized by a dramatic increase in Kondo temperature and associated valence fluctuations below a first-order valence transition at T≃42 K. The bulk-sensitive, element-specific, and valence-projected charge excitation spectra reveal an unusual quasigap in the Yb-derived state density which drives an instability of the electronic structure and renormalizes the low-energy effective Hamiltonian at the transition. Our results provide long-sought experimental evidence for a link between temperature-driven changes in the low-energy Kondo scale and the higher-energy electronic structure of this system.

Na2IrO3 as a novel relativistic Mott insulator with a 340-meV gap.

We study Na2IrO3 by angle-resolved photoemission spectroscopy, optics, and band structure calculations in the local-density approximation (LDA). The weak dispersion of the Ir 5d-t(2g) manifold highlights the importance of structural distortions and spin-orbit (SO) coupling in driving the system closer to a Mott transition. We detect an insulating gap Δ(gap)≃340 meV which, at variance with a Slater-type description, is already open at 300 K and does not show significant temperature dependence even across T(N)≃15 K. An LDA analysis with the inclusion of SO and Coulomb repulsion U reveals that, while the prodromes of an underlying insulating state are already found in LDA+SO, the correct gap magnitude can only be reproduced by LDA+SO+U, with U=3 eV. This establishes Na2IrO3 as a novel type of Mott-like correlated insulator in which Coulomb and relativistic effects have to be treated on an equal footing.

Measurement of magnetic excitations in the two-dimensional antiferromagnetic Sr2CuO2Cl2 insulator using resonant x-ray scattering: evidence for extended interactions.

We measured the momentum dependence of magnetic excitations in the model spin-1/2 2D antiferromagnetic insulator Sr2CuO2Cl2 (SCOC). We identify a single-spin-wave feature and a multimagnon continuum, with different polarization dependences. The spin waves display a large (70 meV) dispersion between the zone-boundary points (π, 0) and (π/2, π/2). Employing an extended t-t'-t''-U one-band Hubbard model, we find significant electronic hopping beyond nearest-neighbor Cu ions, indicative of extended magnetic interactions. The spectral line shape at (π, 0) indicates sizable quantum effects in SCOC and probably more generally in the cuprates.

Unraveling the nature of charge excitations in La2CuO4 with momentum-resolved Cu K-edge resonant inelastic x-ray scattering.

The results of model calculations using exact diagonalization reveal the orbital character of states associated with different Raman loss peaks in Cu K-edge resonant inelastic x-ray scattering (RIXS) from La2CuO4. The model includes electronic orbitals necessary to highlight the nonlocal Zhang-Rice singlet, charge transfer, and d-d excitations, as well as states with apical oxygen 2p(z) character. The dispersion of these excitations is discussed with prospects for resonant final state wave-function mapping. A good agreement with experiments emphasizes the substantial multiorbital character of RIXS profiles in the energy transfer range 1-6 eV.

Soft manifold dynamics behind negative thermal expansion.

Minimal models are developed to examine the origin of large negative thermal expansion in underconstrained systems. The dynamics of these models reveals how underconstraint can organize a thermodynamically extensive manifold of low-energy modes which not only drives negative thermal expansion but extends across the Brillioun zone. Mixing of twist and translation in the eigenvectors of these modes, for which in ZrW2O8 there is evidence from infrared and neutron scattering measurements, emerges naturally in our model as a signature of the dynamics of underconstraint.

Charge-transfer excitations in the model superconductor HgBa(2)CuO(4+delta).

We report a Cu -edge resonant inelastic x-ray scattering (RIXS) study of charge-transfer excitations in the 2-8 eV range in the structurally simple compound HgBa(2)CuO(4+delta) at optimal doping (T(c)=96.5 K). The spectra exhibit a significant dependence on the incident photon energy which we carefully utilize to resolve a multiplet of weakly dispersive (<0.5 eV) electron-hole excitations, including a mode at 2 eV. The observation of this 2 eV excitation suggests the existence of a remnant charge-transfer gap deep in the superconducting phase. Quite generally, our results, which include additional data for the Mott insulator La(2)CuO(4), demonstrate the importance of exploring the incident photon-energy dependence of the RIXS cross section.