Phase Diagrams of Arsenic, Antimony, and Bismuth at Pressures up to 70 kbars

Klement, William; Jayaraman, A.; Kennedy, George C.

doi:10.1103/physrev.131.632

Cited by 131 publications

(69 citation statements)

References 22 publications

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“…The melting temperature drops from 904 K at ambient to about 830 K at 5 to 5.7 GPa (the triple point between liquid, Sb-I and high pressure phase). 25,26 Within a 'single-phase' approach to melting and in the spirit of the Lindemann melting criterium, a microscopic explanation of the negative melting slope would have to take into account that at least part of the phonon spectrum softens considerably with increasing pressure. The second remark concerns the pressure-induced superconductivity of antimony.…”

Section: A7mentioning

confidence: 99%

Effect of pressure on the Raman modes of antimony

et al. 2006

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The effect of pressure on the zone-center optical phonon modes of antimony in the A7 structure has been investigated by Raman spectroscopy. The Ag and Eg frequencies exhibit a pronounced softening with increasing pressure, the effect being related to a gradual suppression of the Peierls-like distortion of the A7 phase relative to a cubic primitive lattice. Also, both Raman modes broaden significantly under pressure. Spectra taken at low temperature indicate that the broadening is at least partly caused by phonon-phonon interactions. We also report results of ab initio frozenphonon calculations of the Ag and Eg mode frequencies. Presence of strong anharmonicity is clearly apparent in calculated total energy versus atom displacement relations. Pronounced nonlinearities in the force versus displacement relations are observed. Structural instabilities of the Sb-A7 phase are briefly addressed in the Appendix.

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Section: A7mentioning

confidence: 99%

Effect of pressure on the Raman modes of antimony

et al. 2006

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“…Bulk Bi-I possesses rich unusual electronic properties, such as high electrical resistance (13,14), large magnetoresistance (15)(16)(17), and unusually great Hall effect (18)(19)(20). Together with its low melting point (6,11), these properties make Bi an important material with wide industrial and engineering applications. The surfaces of Bi-I single crystals are a much better metal than the bulk because of the existence of electronic surface states crossing the Fermi level (21).…”

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confidence: 99%

Deep melting reveals liquid structural memory and anomalous ferromagnetism in bismuth

Shu

Wang

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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As an archetypal semimetal with complex and anisotropic Fermi surface and unusual electric properties (e.g., high electrical resistance, large magnetoresistance, and giant Hall effect), bismuth (Bi) has played a critical role in metal physics. In general, Bi displays diamagnetism with a high volumetric susceptibility (∼10 −4 ). Here, we report unusual ferromagnetism in bulk Bi samples recovered from a molten state at pressures of 1.4-2.5 GPa and temperatures above ∼1,250 K. The ferromagnetism is associated with a surprising structural memory effect in the molten state. On heating, low-temperature Bi liquid (L) transforms to a more randomly disordered high-temperature liquid (L ) around 1,250 K. By cooling from above 1,250 K, certain structural characteristics of liquid L are preserved in L. Bi clusters with characteristics of the liquid L motifs are further preserved through solidification into the Bi-II phase across the pressure-independent melting curve, which may be responsible for the observed ferromagnetism.bismuth | high pressure | ferromagnetism | melt structure B ismuth (Bi) has played important roles in metal and condensed matter physics. The extremely low carrier density of Bi allows quantum limits of the Landau level to be studied under high magnetic field (1) and quantum size effects to be observed at ∼100-nm length scale (2). At ambient condition, Bi is known to crystallize in the rhombohedral A-7 type structure (space group R-3m, D 5 3d ), with the primitive unit cell containing two atoms at positions (u, u, u) and (−u, −u, −u). Each atom has three equidistant nearest neighbors tightly bonded at a distance of ∼3.062Å (3). The Bi4 motifs form puckered bilayers ( Fig. S1A) with a thickness of 1.59Å stacked along the rhombohedral [111] direction. The distance between adjacent bilayers is 2.35Å (4), slightly smaller than the next nearest distance of 3.512Å (5). Each atom's next nearest neighbors are in the adjacent bilayers, and the bonding within each bilayer is much stronger than the interbilayer bonding. As such, Bi exhibits rather complex interatomic binding, with coexisting covalent (within the bilayers), metallic, and weaker van der Waals-like (between bilayers) bonding (4).The phase diagram of Bi is rich and complex ( Fig. 1). At ambient pressure, Bi melts at 544 K (6) with a liquid-liquid transition at 1,010 K (7). With increasing pressure, Bi undergoes structural transitions in both solid and liquid states. The A-7 structured Bi-I phase transforms successively into the monoclinic (Bi-II), incommensurate host-guest (Bi-III), and body-centered cubic (Bi-V) phases (8-10) with increasing pressure to ∼6 GPa. On pressure release, these high-pressure metallic crystalline phases are unstable and revert to the Bi-I phase. Below ∼1.6 GPa, the melting temperature of Bi-I decreases with increasing pressure, a behavior similar to that of ice. Between 1.6 and 2.4 GPa (11), the solid just below melting is the Bi-II phase, which has a similar bilayer structure to that of Bi-I, except that the distance betwe...

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“…That is, it is predicated that at 423 K, the Peierls barrier of the slip systems including covalent bonds is lowered and the differences in critical resolved shear stresses for any slip systems have already disappeared. According to the pressure-temperature phase diagram of bismuth, the phase at high temperature/pressure transits from semimetal to metal, while the phase does not shift to metal under normal pressure 20,21) . This means that at 423 K under normal pressure, a phase shift to metal does not occurs but covalent bonds exist inside the crystals.…”

Section: Resultsmentioning

confidence: 99%