Jack Simonson

From antiferromagnetic insulator to correlated metal in pressurized and doped LaMnPO

Widespread adoption of superconducting technologies awaits the discovery of new materials with enhanced properties, especially higher superconducting transition temperatures Tc. The unexpected discovery of high Tc superconductivity in cuprates suggests that the highest Tcs occur when pressure or doping transform the localized and moment-bearing electrons in antiferromagnetic insulators into itinerant carriers in a metal, where magnetism is preserved in the form of strong correlations. The absence of this transition in Fe-based superconductors may limit their Tcs, but even larger Tcs may be possible in their isostructural Mn analogs, which are antiferromagnetic insulators like the cuprates. It is generally believed that prohibitively large pressures would be required to suppress the effects of the strong Hund’s rule coupling in these Mn-based compounds, collapsing the insulating gap and enabling superconductivity. Indeed, no Mn-based compounds are known to be superconductors. The electronic structure calculations and X-ray diffraction measurements presented here challenge these long held beliefs, finding that only modest pressures are required to transform LaMnPO, isostructural to superconducting host LaFeAsO, from an antiferromagnetic insulator to a metallic antiferromagnet, where the Mn moment vanishes in a second pressure-driven transition. Proximity to these charge and moment delocalization transitions in LaMnPO results in a highly correlated metallic state, the familiar breeding ground of superconductivity.

CaMn2Sb2: Spin waves on a frustrated antiferromagnetic honeycomb lattice

We present inelastic neutron scattering measurements of the antiferromagnetic insulator CaMn2Sb2:, which consists of corrugated honeycomb layers of Mn. The dispersion of magnetic excitations has been measured along the H and L directions in reciprocal space, with a maximum excitation energy of ≈ 24 meV. These excitations are well described by spin waves in a Heisenberg model, including first and second neighbor exchange interactions, J1 and J2, in the Mn plane and also an exchange interaction between planes. The determined ratio J2/J1 ≈ 1/6 suggests that CaMn2Sb2: is the first example of a compound that lies very close to the mean field tricritical point, known for the classical Heisenberg model on the honeycomb lattice, where the N´eel phase and two different spiral phases coexist. The magnitude of the determined exchange interactions reveal a mean field ordering temperature ≈ 4 times larger than the reported N´eel temperature TN = 85 K, suggesting significant frustration arising from proximity to the tricritical point.

Magnetic structure of Yb2Pt2Pb: Ising moments on the Shastry-Sutherland lattice

Here, we have synthesized single crystals of Yb2Pt2Pb, which crystallize in the layered U2Pt2Sn-type structure, where planes of Yb ions lie on a triangular network. Here, we report the results of magnetization, specific heat, and electrical resistivity experiments. The lattice constants and high temperature magnetic susceptibility indicate that the Yb ions are trivalent, while the Schottky peaks in the specific heat show that the ground state is a well isolated doublet. A significant magnetic anisotropy is observed, with the ratio of susceptibilities perpendicular and parallel to the magnetic planes differing by as much as a factor of 30 at the lowest temperatures. Antiferromagnetic order occurs at a Neel temperature TN = 2.07 K. Evidence of short range magnetic fluctuations is found in the magnetic susceptibility and electrical resistivity, which have broad peaks above TN, and in the slow development of the magnetic entropy at TN. Our experiments indicate that Yb2Pt2Pb is a quasi-two-dimensional and localized moment system, where strong magnetic frustration may arise from the geometry of the underlying Shastry-Sutherland lattice.

Observation of antiferromagnetic order collapse in the pressurized insulator LaMnPO

The emergence of superconductivity in the iron pnictide or cuprate high temperature superconductors usually accompanies the suppression of a long-ranged antiferromagnetic (AFM) order state in a corresponding parent compound by doping or pressurizing. A great deal of effort by doping has been made to find superconductivity in Mn-based compounds, which are thought to bridge the gap between the two families of high temperature superconductors, but the AFM order was not successfully suppressed. Here we report the first observations of the pressure-induced elimination of long-ranged AFM order at ~ 34 GPa and a crossover from an AFM insulating to an AFM metallic state at ~ 20 GPa in LaMnPO single crystals that are iso-structural to the LaFeAsO superconductor by in-situ high pressure resistance and ac susceptibility measurements. These findings are of importance to explore potential superconductivity in Mn-based compounds and to shed new light on the underlying mechanism of high temperature superconductivity.

Combined computational and experimental investigation of the La2CuO4–xSx (0 ≤ x ≤ 4) quaternary system

Significance Discovery of new materials enabling new technologies, from novel electronics to better magnets, has so far relied on serendipity. Computational advances show promise that new materials can be designed in a computer and not in the lab, a proposal called “Materials by Design.” We present here a detailed comparison between theory and experiment, carrying out the synthesis of a high-temperature superconductor in an X-ray beam to elucidate the sequence of chemical reactions as the compound forms. Parallel computations of the stabilities of possible compounds that could form from the selected elements accurately predict the observed reactions. Paired with our chemical intuition, this methodology provides understanding and potentially control of the essential chemical principles responsible for stabilizing virtually any compound. The lack of a mechanistic framework for chemical reactions forming inorganic extended solids presents a challenge to accelerated materials discovery. We demonstrate here a combined computational and experimental methodology to tackle this problem, in which in situ X-ray diffraction measurements monitor solid-state reactions and deduce reaction pathways, while theoretical computations rationalize reaction energetics. The method has been applied to the La2CuO4−xSx (0 ≤ x ≤ 4) quaternary system, following an earlier prediction that enhanced superconductivity could be found in these new lanthanum copper(II) oxysulfide compounds. In situ diffraction measurements show that reactants containing Cu(II) and S(2−) ions undergo redox reactions, leaving their ions in oxidation states that are incompatible with forming the desired new compounds. Computations of the reaction energies confirm that the observed synthetic pathways are indeed favored over those that would hypothetically form the suggested compounds. The consistency between computation and experiment in the La2CuO4−xSx system suggests a role for predictive theory: to identify and to explicate new synthetic routes for forming predicted compounds.

Synthesis and crystal structure of La21Cr8−2aAlbGe7−bC12 [a = 0.22 (2) and b = 0.758 (19)]

The face-centered cubic crystal structure of a new multinary chromium carbide, La21Cr8−2aAlbGe7−bC12, is composed of isolated and geometrically frustrated regular Cr tetrahedra that are co-centered within regular C octahedra. These mutually separated Cr4−aC6 clusters are distributed throughout a three-dimensional framework of Al, Ge, and La.