Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr2IrO4.

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity. Recently, photo-excitation has been used to induce similarly exotic states transiently. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr2IrO4. We find that the non-equilibrium state, 2 ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. The marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.

Local vibrations and negative thermal expansion in ZrW2O8.

We present an x-ray pair distribution function (XPDF) analysis and extended x-ray absorption fine structure (EXAFS) data for ZrW2O8 (10-500 K) with a focus on the stiffness of the Zr-O-W linkage. The XPDF is highly sensitive to W-Zr and W-W correlations, but much less so to O-O or W-O correlations. The Zr-W peak in the XPDF data has a weak temperature dependence and, hence, this linkage is relatively stiff and does not permit bending of the Zr-O-W link. We propose that the low energy vibrational modes that lead to negative thermal expansion involve correlated rotations of ZrO6 octahedra that produce large <111> translations of the WO4 tetrahedra, rather than a transverse motion of O atoms that imply a flexible Zr-O-W linkage.

Cu(Ir1 - xCrx)2S4: a model system for studying nanoscale phase coexistence at the metal-insulator transition.

Increasingly, nanoscale phase coexistence and hidden broken symmetry states are being found in the vicinity of metal-insulator transitions (MIT), for example, in high temperature superconductors, heavy fermion and colossal magnetoresistive materials, but their importance and possible role in the MIT and related emergent behaviors is not understood. Despite their ubiquity, they are hard to study because they produce weak diffuse signals in most measurements. Here we propose Cu(Ir1 - xCrx)2S4 as a model system, where robust local structural signals lead to key new insights. We demonstrate a hitherto unobserved coexistence of an Ir(4+) charge-localized dimer phase and Cr-ferromagnetism. The resulting phase diagram that takes into account the short range dimer order is highly reminiscent of a generic MIT phase diagram similar to the cuprates. We suggest that the presence of quenched strain from dopant ions acts as an arbiter deciding between the competing ground states.

The Liga algorithm for ab initio determination of nanostructure.

Computational techniques for nanostructure determination of substances that resist standard crystallographic methods are often laborious processes starting from initial guess solutions not derived from experimental data. The Liga algorithm can create nanostructures using only lists of lengths or distances between atom pairs, providing an experimental basis for starting structures. These distance lists may be extracted from a variety of experimental probes and we illustrate the procedure with distances determined from the pair distribution function. Candidate subclusters that are a subset of a structure's atoms compete based on adherence to the length list. Atoms are added to well performing candidates and removed from poor ones, until a complete structure with sufficient agreement to the length list emerges. The Liga algorithm is shown to reliably recreate Lennard-Jones clusters from ideal length lists and the C60 structure from neutron-scattering data. The correct fullerene structure was obtained with experimental data which missed several distances and had loosened constraints on distance multiplicity. This suggests that the Liga algorithm may have robust applicability for a wide range of nanostructures even in the absence of ideal data.

PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals.

PDFfit2 is a program as well as a library for real-space refinement of crystal structures. It is capable of fitting a theoretical three-dimensional (3D) structure to atomic pair distribution function data and is ideal for nanoscale investigations. The fit system accounts for lattice constants, atomic positions and anisotropic atomic displacement parameters, correlated atomic motion, and experimental factors that may affect the data. The atomic positions and thermal coefficients can be constrained to follow the symmetry requirements of an arbitrary space group. The PDFfit2 engine is written in C++ and is accessible via Python, allowing it to inter-operate with other Python programs. PDFgui is a graphical interface built on the PDFfit2 engine. PDFgui organizes fits and simplifies many data analysis tasks, such as configuring and plotting multiple fits. PDFfit2 and PDFgui are freely available via the Internet.

Ab initio determination of solid-state nanostructure.

Advances in materials science and molecular biology followed rapidly from the ability to characterize atomic structure using single crystals. Structure determination is more difficult if single crystals are not available. Many complex inorganic materials that are of interest in nanotechnology have no periodic long-range order and so their structures cannot be solved using crystallographic methods. Here we demonstrate that ab initio structure solution of these nanostructured materials is feasible using diffraction data in combination with distance geometry methods. Precise, sub-ångström resolution distance data are experimentally available from the atomic pair distribution function (PDF). Current PDF analysis consists of structure refinement from reasonable initial structure guesses and it is not clear, a priori, that sufficient information exists in the PDF to obtain a unique structural solution. Here we present and validate two algorithms for structure reconstruction from precise unassigned interatomic distances for a range of clusters. We then apply the algorithms to find a unique, ab initio, structural solution for C60 from PDF data alone. This opens the door to sub-ångström resolution structure solution of nanomaterials, even when crystallographic methods fail.