Superconductivity-Electron Count Relationship in Heusler Phases-the Case of LiPd2Si.

We report superconductivity in the full Heusler compound LiPd2Si (space group Fm3̅m, No. 225) at a critical temperature of Tc = 1.3 K and a normalized heat capacity jump at Tc, ΔC/γTc = 1.1. The low-temperature isothermal magnetization curves imply type-I superconductivity, as previously observed in LiPd2Ge. We show, based on density functional theory calculations and using the molecular orbital theory approach, that while LiPd2Si and LiPd2Ge share the Pd cubic cage motif that is found in most of the reported Heusler superconductors, they show distinctive features in the electronic structure. This is due to the fact that Li occupies the site which, in other compounds, is filled with an early transition metal or a rare-earth metal. Thus, while a simple valence electron count-property relationship is useful in predicting and tuning Heusler materials, inclusion of the symmetry of interacting frontier orbitals is also necessary for the best understanding.

Chemistry of Quantum Spin Liquids.

Quantum spin liquids are an exciting playground for exotic physical phenomena and emergent many-body quantum states. The realization and discovery of quantum spin liquid candidate materials and associated phenomena lie at the intersection of solid-state chemistry, condensed matter physics, and materials science and engineering. In this review, we provide the current status of the crystal chemistry, synthetic techniques, physical properties, and research methods in the field of quantum spin liquids. We highlight a number of specific quantum spin liquid candidate materials and their structure-property relationships, elucidating their fascinating behavior and connecting it to the intricacies of their structures. Furthermore, we share our thoughts on defects and their inevitable presence in materials, of which quantum spin liquids are no exception, which can complicate the interpretation of characterization of these materials, and urge the community to extend their attention to materials preparation and data analysis, cognizant of the impact of defects. This review was written with the intention of providing guidance on improving the materials design and growth of quantum spin liquids, and to paint a picture of the beauty of the underlying chemistry of this exciting class of materials.

Dynamical Bonding Driving Mixed Valency in a Metal Boride.

Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed-valent semiconductor, and later a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB6 centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm-B bonding modes within SmB6 , corresponding to different oxidation states of the Sm. The mixed valency arises in SmB6 from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure-induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

(Cs X)Cu5O2(PO4)2 ( X = Cl, Br, I): A Family of Cu2+ S = 1/2 Compounds with Capped-Kagomé Networks Composed of OCu4 Units.

Three new salt inclusion compounds (Cs X)Cu5O2(PO4)2 ( X = Cl, Br, I), phosphate analogues of the kagomé mineral averievite, are reported. Their crystal structures are composed of trigonal networks of corner-sharing OCu4 anion-centered tetrahedra, forming capped-kagomé planes, which can also be regarded as two-dimensional slices along the [111] direction of a pyrochlore lattice. Magnetization and heat capacity measurements reveal strong geometric frustration of this network and complex magnetic behavior. X-ray and neutron diffraction studies show that all three compounds undergo a trigonal-to-monoclinic phase transition upon cooling, with a first-order phase transition seen in CsBr and CsI analogues. Along with the previously reported (CsCl)Cu5O2(VO4)2, these three new compounds belong to a large family of OCu4-based networks, which are a playground for studying frustrated quantum magnetism.

Universal Single-Ion Physics in Spin-Orbit-Coupled d5 and d4 Ions.

We have identified six new 4d4 and 4d5 compounds with isolated RuCl6 octahedra, with formulas (HMA)4RuCl6·Cl (1; MA = methylamine), (HGly)4RuCl6·Cl (2; gly = glycine), (HGly)3RuCl6·2H2O (3), (NH4)2RuCl6 (4), (HPy)2RuCl6 (5; py = pyridine), and H2(4,4'-bpy)RuCl6 (6; 4,4'-bpy = 4,4'-bipyridine). We find that the temperature-dependent magnetization is well described by single-ion physics in the presence of spin-orbit coupling and negligible superexchange interactions. Further, we find that many compounds in the literature are also well described by single-ion physics, and our results demonstrate the importance of considering single-ion physics when evaluating candidate geometric frustrated magnets in the presence of spin-orbit coupling.

Progress toward Solid State Synthesis by Design.

Ages of history are defined by the underlying materials that promoted human development: stone, bronze, and iron ages. Since the middle of the last century, humanity has lived in a silicon age, where the development of the transistor ushered in new technologies previously thought inconceivable. But as technology has advanced, so have the requirements for new materials to sustain increasing physical demands. The field of solid state chemistry is dedicated to the discovery of new materials and phenomena, and though most materials discoveries in history have been through serendipity rather than careful reaction design, the last few decades have seen an increase in the number of materials discovered through a consideration of chemical reaction kinetics and thermodynamics. Materials by design have changed the way solid state chemists approach the synthesis of possible materials with interesting and useful properties. Unlike other chemistry subfields such as organic chemistry and biochemistry, solid state chemistry does not currently benefit from a toolbox of reactions that can allow for the synthesis of any arbitrary material. The diversity and complexity of the solid state phase space likely inhibits chemists from ever having such a toolbox. However, a thorough understanding of the various synthetic techniques involved in the synthesis of stable and metastable solids may be realized through an understanding of the reaction kinetics and thermodynamics. In the Account, we review the common synthesis techniques involved in the formation of metastable materials and break down their underlying chemistry to the simplest reaction mechanisms involved. The synthesis reactions of most metastable materials can be understood through these three reaction driving parameters, which include the exploitation of Le Chatelier's principle, thermo-kinetic reaction coupling, and lowering the activation energy of formation of the metastable product, and we identify several materials whose syntheses are described either by one or a combination of these driving parameters. We identify what exists at the frontier of materials discovery by design, including novel applications of supercritical fluids for tuning between "gas" and "solvent"-like environments. While conventional solvation requires changes in either the temperature or composition of the system, supercritical fluid solvation requires only changes in the fluid density, which opens up the possibilities for the synthesis of new materials. Most importantly, however, we look toward the future of materials synthesis by design and see that it must be a collaborative one. At present, chemists design materials using knowledge about chemical structure and reactivity but often target specific materials with very specific properties. In contrast, computational chemists perform calculations on millions of different elemental combinations and find many candidates of possible materials with interesting properties, though most of these are not realizable synthetically due to limitations in reactivity, kinetics, or thermodynamics. Synthetic harmony can be achieved through active collaboration and communication between these two subfields of chemistry, such that new calculations can incorporate complete knowledge about reaction kinetics and thermodynamics, and new syntheses target computationally predicted materials derived from an understanding of mapped reaction landscapes.