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We present a computational study of the electronic structure and lattice dynamics of IrTe2 that sheds light on the debated mechanism of the temperature-induced phase transitions of this material. At ambient temperature, IrTe2 adopts a hexagonal crystal structure typical of metal chalcogenides. Upon cooling, some Ir–Ir distances shorten, thus inducing lattice modulations. We demonstrate that this is due to the formation of multicenter bonds involving both Ir and Te atoms. We show how the formation of these bonds is energetically favorable but lowers the vibrational entropy; therefore, they are destabilized by temperature. The obtained model is exploited to rationalize the effect of Se doping and other experimental results from the literature.

The mechanism of silver-oxygen and silver-sulfur reactions is revealed by means of molecular dynamics simulations, performed with reactive force fields purposely built and extensively tested against quantum-chemical results. Different reaction mechanisms and rates for Ag-O and Ag-S emerge. This study solves the long-lasting question why silver exposed to the environment is strongly vulnerable to sulfur corrosion (tarnishing) but hardly reacts with O2 , despite the thermodynamic prediction that both oxide and sulfide should form. The reliability of the simulation results is confirmed by the agreement with a multitude of experimental results from the literature.

The unique combination of organic and inorganic layers in 2D layered perovskites offers promise for the design of a variety of materials for mechatronics, flexoelectrics, energy conversion, and lighting. However, the potential tailoring of their properties through the organic building blocks is not yet well understood. Here, different classes of organoammonium molecules are exploited to engineer the optical emission and robustness of a new set of Ruddlesden-Popper metal-halide layered perovskites. It is shown that the type of molecule regulates the number of hydrogen bonds that it forms with the edge-sharing [PbBr6 ]4- octahedra layers, leading to strong differences in the material emission and tunability of the color coordinates, from deep-blue to pure-white. Also, the emission intensity strongly depends on the length of the molecules, thereby providing an additional parameter to optimize their emission efficiency. The combined experimental and computational study provides a detailed understanding of the impact of lattice distortions, compositional defects, and the anisotropic crystal structure on the emission of such layered materials. It is foreseen that this rational design can be extended to other types of organic linkers, providing a yet unexplored path to tailor the optical and mechanical properties of these materials and to unlock new functionalities.

The application of high pressure (hundreds of gigapascals) to materials, besides modifying their properties, changes dramatically their reactivity. Consequently, new compounds are formed, which violate the chemical paradigms known to date. In fact, it was recently discovered (Zhang et al., Science, 2013) that sodium subchlorides (NaxCl, x > 1) become stable at high pressure. In this work, we carry out a thorough study of these compounds as well as of other alkali subhalides by means of evolutionary crystal structure prediction calculations combined with an in-depth analysis of their crystal and electronic structures. The results of our investigation are threefold. We present an updated phase diagram of NaxCl, including one new compound (Na4Cl3) and two previously undiscovered phases of Na3Cl. We demonstrate the appearance of remarkable features in the electronic structure of sodium subchlorides, such as chlorine atoms acquiring a −2 oxidation state. Most importantly, we derive a model which enables one to rationalize the stability of alkali subhalides at high pressure. The predictive ability of our model was validated by the results of crystal structure prediction calculations we carried out on alkali subhalides A3Y (A = Li, Na, K; Y = F, Cl, Br). Moreover, we show how the stability of recently reported high-pressure compounds can be rationalized on the basis of the insights gained in the present study.

The chemistry of the elements is heavily altered by high pressure, with stabilization of many new and often unexpected compounds, the emergence of which can profoundly change models of planetary interiors, where high pressure reigns. The C-H-O system is one of the most important planet-forming systems, but its high-pressure chemistry is not well known. Here, using state-of-the-art variable-composition evolutionary searches combined with quantum-mechanical calculations, we explore the C-H-O system at pressures up to 400 GPa. Besides uncovering new stable polymorphs of high-pressure elements and known molecules, we predicted the formation of new compounds. A 2CH4:3H2 inclusion compound forms at low pressure and remains stable up to 215 GPa. Carbonic acid (H2CO3), highly unstable at ambient conditions, was predicted to form exothermically at mild pressure (about 1 GPa). As pressure rises, it polymerizes and, above 314 GPa, reacts with water to form orthocarbonic acid (H4CO4). This unexpected high-pressure chemistry is rationalized by analyzing charge density and electron localization function distributions and implications for general chemistry and planetary science are also discussed.

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes this material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na8 cubes. We also predict the existence of Na2HeO with a similar structure at pressures above 15 GPa.

Ag and Sn are the major components of solder alloys adopted to assemble printed circuit boards. The qualities that make them the alloys of choice for the modern electronic industry are related to their physical and chemical properties. For corrosion resistance and solderability, surface properties are particularly important. Yet, atomic-level information about the surfaces of these alloys is not known. Here we fill this gap by presenting an extensive ab initio investigation of composition, energetics, structure and reactivity of Ag-Sn alloy surfaces. The structure and stability of various surfaces is evaluated, and the main factors determining the energetics of surface formation are uncovered. Oxygen and sulphur chemisorptions are studied and discussed in the framework of corrosion tendency, an important issue for printed circuit boards. Adsorption energy trends are rationalized based on the analysis of structural and electronic features.