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Register a new userPhase stability of lanthanum orthovanadate at high-pressure
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When monoclinic monazite-type LaVO4 (space group P21/n) is squeezed up to 12 GPa at room temperature, a phase transition to another monoclinic phase has been found. The structure of the high-pressure phase of LaVO4 is indexed with the same space group (P21/n), but with a larger unit-cell in which the number of atoms is doubled. The transition leads to an 8% increase in the density of LaVO4. The occurrence of such a transition has been determined by x-ray diffraction, Raman spectroscopy, and ab initio calculations. The combination of the three techniques allows us to also characterize accurately the pressure evolution of unit-cell parameters and the Raman (and IR)-active phonons of the low- and high-pressure phase. In particular, room-temperature equations of state have been determined. The changes driven by pressure in the crystal structure induce sharp modifications in the color of LaVO4 crystals, suggesting that behind the monoclinic-to-monoclinic transition there are important changes of the electronic properties of LaVO4.
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Lanthanum (La), the first member of the rare-earth elements, recently aroused strong interest due to its unique superhydride with superconducting properties. Although there is much theoretical and experimental work about phase transitions and superconductivity in metallic La, we got a new body-centred tetragonal ($bct$) phase in metallic La with space group $I4/mmm$ at $190$ GPa exchanging from face-centered cubic ($fcc$) phase in previous work, which expanded the phase transition sequence. The $bct$ phase shows an abnormal packing way that turned to non-closed packing at high pressure. And more detailed properties of the new phase are discussed.
X-ray diffraction and Raman scattering measurements, and first-principles calculations are performed to search for the formation of NaCl-hydrogen compound. When NaCl and H$_{2}$ mixture is laser-heated to above 1500 K at pressures exceeding 40 GPa, we observed the formation of NaClH$_{textit{x}}$ with $textit{P}$6$_{3}$/$textit{mmc}$ structure which accommodates H$_{2}$ molecules in the interstitial sites of NaCl lattice forming ABAC stacking. Upon the decrease of pressure at 300 K, NaClH$_textit{x}$ remains stable down to 17 GPa. Our calculations suggest the observed NaClH$_{textit{x}}$ is NaCl(H$_{2}$). Besides, a hydrogen-richer phase NaCl(H$_{2}$)$_{4}$ is predicted to become stable at pressures above 40 GPa.
AgClO4 has been studied under compression by x-ray diffraction and density functional theory calculations. Experimental evidence of a structural phase transition from the tetragonal structure of AgClO4 to an orthorhombic barite-type structure has been found at 5.1 GPa. The transition is supported by total-energy calculations. In addition, a second transition to a monoclinic structure is theoretically proposed to take place beyond 17 GPa. The equation of state of the different phases is reported as well as the calculated Raman-active phonons and their pressure evolution. Finally, we provide a description of all the structures of AgClO4 and discuss their relationships. The structures are also compared with those of AgCl in order to explain the structural sequence determined for AgClO4.
In the search for MgB2-like phonon-mediated superconductors we have carried out a systematic density functional theory study of the Ca-B system, isoelectronic to Mg-B, at ambient and gigapascal pressures. A remarkable variety of candidate high-pressure ground states have been identified with an evolutionary crystal structure search, including a stable alkaline-earth monoboride oI8-CaB, a superconductor with an expected critical temperature (Tc) of 5.5 K. We have extended our previous study of CaB6 [Phys. Rev. Lett. 108, 102501 (2012)] to nearby stoichiometries of CaB[6+x], finding that extra boron further stabilizes the proposed B24 units. Here an explanation is given for the transformation of cP7-CaB6 into the more complex oS56 and tI56 polymorphs at high pressure. The stability of the known metallic tP20 phase of CaB4 at ambient pressure is explained from a crystal structure and chemical bonding point of view. The tP20 structure is shown to destabilize at 19 GPa relative to a semiconducting MgB4-like structure due to chemical pressure from the metal ion. The hypothetical AlB2-type structure of CaB2, previously shown to have favorable superconducting features, is demonstrated here to be unstable at all pressures; two new metallic CaB2 polymorphs with unusual boron networks stabilize at elevated pressures above 8 GPa but are found to have very low critical temperatures (Tc ~1 K). The stability of all structures has been rationalized through comparison with alkaline-earth analogs, emphasizing the importance of the size of the metal ion for the stability of borides. Our study illustrates the inverse correlation between the thermodynamic stability and superconducting properties and the necessity to carefully examine both in the design of new synthesizable superconducting materials.
Transition metal nitrides have attracted much interest of the scientific community for their intriguing properties and technological applications. Here we focus on yttrium dinitride (YN$_{2}$) and its formation and structural transition under pressure. We employed a fixed composition USPEX search to find the most stable polymorphs. We choose yttrium as a proxy for the lanthanide series because it has only $+3$ oxidation state, contrary to most transition metals. We then computed thermodynamic and dynamical stability of these structures compared to the decomposition reactions and we found that the compound undergoes two structural transitions, the latter showing the formation N$_{4}$ chains. A closer look into the nature of the nitrogen bonding showed that in the first two structures, where nitrogen forms dimers, the bond length is intermediate between that of a single bond and that of a double bond, making it hard to rationalize the proper oxidation state configuration for YN$_{2}$. In the latter structure where there is the formation of N$_{4}$ chains, the bond lengths increase significantly, up to a value that can be justified as a single bond. Finally, we also studied the electronic structure and the dynamical stability of the structures we found.
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