Local structure, thermodynamics, and melting of boron phosphide at high pressures by deep learning-driven ab initio simulations.

Boron phosphide (BP) is a (super)hard semiconductor constituted of light elements, which is promising for high demand applications at extreme conditions. The behavior of BP at high temperatures and pressures is of special interest but is also poorly understood because both experimental and conventional ab initio methods are restricted to studying refractory covalent materials. The use of machine learning interatomic potentials is a revolutionary trend that gives a unique opportunity for high-temperature study of materials with ab initio accuracy. We develop a deep machine learning potential (DP) for accurate atomistic simulations of the solid and liquid phases of BP as well as their transformations near the melting line. Our DP provides quantitative agreement with experimental and ab initio molecular dynamics data for structural and dynamic properties. DP-based simulations reveal that at ambient pressure, a tetrahedrally bonded cubic BP crystal melts into an open structure consisting of two interpenetrating sub-networks of boron and phosphorous with different structures. Structure transformations of BP melt under compressing are reflected by the evolution of low-pressure tetrahedral coordination to high-pressure octahedral coordination. The main contributions to structural changes at low pressures are made by the evolution of medium-range order in the B-subnetwork and, at high pressures, by the change of short-range order in the P-subnetwork. Such transformations exhibit an anomalous behavior of structural characteristics in the range of 12-15 GPa. DP-based simulations reveal that the Tm(P) curve develops a maximum at P ≈ 13 GPa, whereas experimental studies provide two separate branches of the melting curve, which demonstrate the opposite behavior. Analysis of the results obtained raises open issues in developing machine learning potentials for covalent materials and stimulates further experimental and theoretical studies of melting behavior in BP.

Structural transformations and thermal stability of RhGe synthesized under high temperature and pressure.

Here, we study B20-type RhGe, a representative of a class of non-centrosymmetric monosilicides and monogermanides, which possess unique topological and magnetic properties important for many possible applications. The stability and phase transitions of the non-equilibrium B20-RhGe phase that can only be obtained under high pressure, are investigated theoretically usingab initiocalculations and experimentally by means of differential scanning calorimetry. For RhGe and, for comparison, for its analogue RhSi, we conducted an evolutionary search for low-energy polymorphic modifications at zero temperature and then performed simulations of their behavior at finite temperatures. The (P,T) conditions of stability for the found polymorphs are determined. Our calorimetric studies on high-pressure-synthesized RhGe samples allowed us to reveal peculiarities in thermal stability and heating-induced phase transformations. X-ray diffraction analysis and microstructure analysis of the samples were carried out before and after the heating. We also determined the specific heat from calorimetric measurements and compared the results with our calculations in the quasi-harmonic approximation.

The hyperfine magnetic fields and the effect of high pressure on the magnetic transition temperatures of the noncentrosymmetric FeRhGe2compound (B20).

Hyperfine parameters and the pressure dependence of the magnetic transition temperatures of FeRhGe2have been investigated. Sample has been prepared using high pressure-high temperature synthesis technique. FeRhGe2consists of two B20 structure phases with close lattice constants. The phase separation stays constant in the temperature range 4-300 K. The magnetic transition temperaturesTc1= 213 K andTc2= 135 K of FeRhGe2slightly increases with pressure in the range 0-4.5 GPa. We have compared this pressure dependence with some others compounds in the family Fe1-xRhxGe. The two phases in FeRhGe2have slightly different values of the hyperfine magnetic fields.

Competition of charge-density waves and superconductivity in sulfur.

A one-dimensional charge-density wave (CDW) instability is shown to be responsible for the formation of the incommensurate modulation of the atomic lattice in the high-pressure phase of sulfur. The coexistence of, and competition between, the CDW and the superconducting state leads to the previously observed increase of T{c} up to 17 K, which we attribute to the suppression of the CDW instability, the same phenomenology found in doped layered dichalcogenides.