Biao Wan

Diverse ruthenium nitrides stabilized under pressure: a theoretical prediction.

First-principles calculations were performed to understand the structural stability, synthesis routes, mechanical and electronic properties of diverse ruthenium nitrides. RuN with a new I-4m2 symmetry stabilized by pressure is found to be energetically preferred over the experimental NaCl-type and ZnS-type ones. The Pnnm-RuN2 is found to be stable above 1.1 GPa, in agreement with the experimental results. Specifically, new stoichiometries like RuN3 and RuN4 are proposed firstly to be thermodynamically stable, and the dynamical and mechanical stabilities of the newly predicted structures have been verified by checking their phonon spectra and elastic constants. A phase transition from P4/mmm-RuN4 to C2/c-RuN4 is also uncovered at 23.0 GPa. Drawn from bonding and band structure analysis, P4/mmm-RuN4 exhibits semi-metal-like behavior and becomes a semiconductor for the high-pressure C2/c-RuN4 phase. Meanwhile the P21/c-RuN3 shows metallic feature. Highly directional covalent N-N and Ru-N bonds are formed and dominating in N-enriched Ru nitrides, making them promising hard materials.

Structural Diversity and Electronic Properties of 3d Transition Metal Tetraphosphides, TMP4 (TM = V, Cr, Mn, and Fe)

Transition-metal (TM) phosphides attract increasing attention with applications for energy conversion and storage, due to their outstanding physical, chemical, and electronic properties. The 3d transition metal tetraphosphides (TMP4, TM = V, Cr, Mn, and Fe) possess multiple allotropies and rich electronic properties. Here, we perform the investigations of the structural, electronic, and elastic properties for 3d-TMP4 (TM = V, Cr, Mn, and Fe) using density functional theory (DFT) calculations. These compounds are featured with alternating buckled phosphorus sheets with ten-numbered phosphorus rings and varied transition-metal layers. Hybrid DFT calculations reveal that TMP4 compounds exhibit a wide range of electrical properties, ranging from metallic behavior for VP4 to semiconducting behavior for CrP4 with the narrow direct band gap of 0.63 eV to enlarged semiconducting MnP4 and FeP4 with band gap of 1.6-2.1 eV. The bonding analysis indicates that P-P and TM-P covalent interactions dominate in the phosphorus sheets and TMP6 octahedrons, which are responsible for the structural and electronic diversity.

Metal-to-Semiconductor Transition and Electronic Dimensionality Reduction of Ca2N Electride under Pressure

Abstract The discovery of electrides, in particular, inorganic electrides where electrons substitute anions, has inspired striking interests in the systems that exhibit unusual electronic and catalytic properties. So far, however, the experimental studies of such systems are largely restricted to ambient conditions, unable to understand their interactions between electron localizations and geometrical modifications under external stimuli, e.g., pressure. Here, pressure‐induced structural and electronic evolutions of Ca2N by in situ synchrotron X‐ray diffraction and electrical resistance measurements, and density functional theory calculations with particle swarm optimization algorithms are reported. Experiments and computation are combined to reveal that under compression, Ca2N undergoes structural transforms from R 3¯ m symmetry to I 4¯2d phase via an intermediate Fd 3¯ m phase, and then to Cc phase, accompanied by the reductions of electronic dimensionality from 2D, 1D to 0D. Electrical resistance measurements support a metal‐to‐semiconductor transition in Ca2N because of the reorganizations of confined electrons under pressure, also validated by the calculation. The results demonstrate unexplored experimental evidence for a pressure‐induced metal‐to‐semiconductor switching in Ca2N and offer a possible strategy for producing new electrides under moderate pressure.

Revealing phase relations between Fe2B7 and FeB4 and hypothetical Fe2B7-type Ru2B7 and Os2B7: first-principles calculations

Investigation of new materials recovered using high pressure can foresee the unobservable structures and bonding of crystals. Employing first-principles calculations, we aim to provide an atomic understanding of the origin of multiple phases and mutual intergrowth for metastable iron borides. The competing FeB4 and Fe2B7 in the experiment are compared by their enthalpy and structural features. The closely similar enthalpy of Fe2B7 + B and Fe2B8 (FeB4) may explain the coexistence and tight mutual intergrowth of these two phases. The hypothetical Ru2B7 and Os2B7 are also suggested by the stability evaluations. The stable Ru2B7 and Os2B7 show an interesting metallic property and a great mechanical property due to the hybridization of metal-d and B-p orbitals and B–B covalent bonding.