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Title: Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP

Abstract

A reversible, displacive, pressure-induced structural phase transition has been found to occur in nickel monophosphide NiP at approximately 3.5 GPa by means of in situ synchrotron single-crystal X-ray diffraction. The new phase, with Pearson symbol oC56, assumes an orthorhombic structure with Cmc2{sub 1} space group and unit cell parameters a=23.801(2) {angstrom}, b=5.9238(6) {angstrom}, and c=4.8479(4) {angstrom} at 5.79 GPa. The high-pressure phase is a superstructure of the ambient, oP16 phase with multiplicity of 3.5. The phosphorous sublattice gradually converts from the net of isolated P{sub 2} dimers found in the ambient NiP, towards zig-zag polymeric P{infinity} chains found in MnP-type structures. The transformation involves development of triatomic phosphorous clusters and interconnected Ni slabs with diamondoid topology. The high-pressure phase, which represents intermediate polymerization step, is a commensurately modulated superstructure of the NiAs aristotype. The phase transformation in NiP bears resemblance to the effect of successive substitution of Si or Ge in place of P found in the series of stoichiometric inhomogeneous linear structures in ternary NiP{sub 1-x}Si{sub x} and NiP{sub 1-x}Ge{sub x} systems.

Authors:
; ;  [1];  [2]
  1. (UC)
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - OTHERNSF
OSTI Identifier:
1022282
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Solid State Chem.; Journal Volume: 184; Journal Issue: (8) ; 08, 2011
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Dera, Przemyslaw, Lazarz, John D., Lavina, Barbara, and UNLV). Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP. United States: N. p., 2016. Web. doi:10.1016/j.jssc.2011.05.050.
Dera, Przemyslaw, Lazarz, John D., Lavina, Barbara, & UNLV). Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP. United States. doi:10.1016/j.jssc.2011.05.050.
Dera, Przemyslaw, Lazarz, John D., Lavina, Barbara, and UNLV). 2016. "Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP". United States. doi:10.1016/j.jssc.2011.05.050.
@article{osti_1022282,
title = {Pressure-induced development of bonding in NiAs type compounds and polymorphism of NiP},
author = {Dera, Przemyslaw and Lazarz, John D. and Lavina, Barbara and UNLV)},
abstractNote = {A reversible, displacive, pressure-induced structural phase transition has been found to occur in nickel monophosphide NiP at approximately 3.5 GPa by means of in situ synchrotron single-crystal X-ray diffraction. The new phase, with Pearson symbol oC56, assumes an orthorhombic structure with Cmc2{sub 1} space group and unit cell parameters a=23.801(2) {angstrom}, b=5.9238(6) {angstrom}, and c=4.8479(4) {angstrom} at 5.79 GPa. The high-pressure phase is a superstructure of the ambient, oP16 phase with multiplicity of 3.5. The phosphorous sublattice gradually converts from the net of isolated P{sub 2} dimers found in the ambient NiP, towards zig-zag polymeric P{infinity} chains found in MnP-type structures. The transformation involves development of triatomic phosphorous clusters and interconnected Ni slabs with diamondoid topology. The high-pressure phase, which represents intermediate polymerization step, is a commensurately modulated superstructure of the NiAs aristotype. The phase transformation in NiP bears resemblance to the effect of successive substitution of Si or Ge in place of P found in the series of stoichiometric inhomogeneous linear structures in ternary NiP{sub 1-x}Si{sub x} and NiP{sub 1-x}Ge{sub x} systems.},
doi = {10.1016/j.jssc.2011.05.050},
journal = {J. Solid State Chem.},
number = (8) ; 08, 2011,
volume = 184,
place = {United States},
year = 2016,
month = 7
}
  • The nickel arsenide (B81) and related crystal structures are among the most important crystallographic arrangements assumed by Fe and Ni compounds with light elements such as Si, O, S, and P, expected to be present in planetary cores. Despite the simple structure, some of these materials like troilite (FeS) exhibit complex phase diagrams and rich polymorphism, involving significant changes in interatomic bonding and physical properties. NiP (oP16) represents one of the two principal structure distortions found in the nickel arsenide family and is characterized by P–P bonding interactions that lead to the formation of P2 dimers. In the current study,more » the single-crystal synchrotron X-ray diffraction technique, aided by first principles density functional theory (DFT) calculations, has been applied to examine the compression behavior of NiP up to 30 GPa. Two new reversible displacive phase transitions leading to orthorhombic high-pressure phases with Pearson symbols oP40 and oC24 were found to occur at approximately 8.5 and 25.0 GPa, respectively. The oP40 phase has the primitive Pnma space group with unit cell a = 4.7729(5) Å, b = 16.6619(12) Å, and c = 5.8071(8) Å at 16.3(1) GPa and is a superstructure of the ambient oP16 phase with multiplicity of 2.5. The oC24 phase has the acentric Cmc21 space group with unit cell a = 9.695(6) Å, b = 5.7101(9) Å, and c = 4.7438(6) Å at 28.5(1) GPa and is a superstructure of the oP16 phase with multiplicity of 1.5. DFT calculations fully support the observed sequence of phase transitions. The two new phases constitute logical next stages of P sublattice polymerization, in which the dilution of the P3 units, introduced in the first high-pressure phase, decreases, leading to compositions of Ni20(P3)4(P2)4 and Ni12(P3)4, and provide important clues to understanding of phase relations and transformation pathways in the NiAs family.« less
  • The electronic band structure and charge densities for two transition metal monosulfides TiS and VS, with the NiAs-type structure have been calculated using the band theoretical Green's function technique. The results of these calculations are interpreted in terms of chemical bonding and stabilization effects in the solid. It is found that the charge density of the transition metal d-like electrons is maximized in the direction through centers of triangular faces of the octahedrally coordinated sulfur atoms, rather than along the c axis between adjacent metal atom layers, a distribution which was originally believed to stabilize the NiAs-type structure.
  • Manganese sulfide (MnS) nanocrystals (NCs) with three different phases were synthesized by one-pot solvent thermal approach. The crystal structures and morphologies were investigated using powder X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. We found that the crystal structure and morphology of MnS NCs could be controlled by simply varying the reaction temperature. The detailed growth process of MnS nanobipods, including the zinc blende (ZB)-core formation and wurtzite (WZ)-arms growth, provides direct experimental evidence for the polymorphism model. Furthermore, we have studied the stability of metastable ZB- and WZ-MnS NCs under high pressure and found that ZB-nanoparticles andmore » ZB/WZ-nanobipods are stable below their critical pressure, 5.3 and 2.9 GPa, respectively. When pressures exceed the critical point, all these metastable MnS NCs directly convert to the stable rock salt MnS.« less
  • Al{sub 3}BC{sub 3}, an isostructural phase to Mg{sub 3}BN{sub 3}, experienced no pressure-induced phase transformation that occurred in the latter material (J. Solid State Chem. 154 (2000) 254-256). The discrepancy is not clear yet. Using the first-principles density functional calculations, we predict that Al{sub 3}BC{sub 3} undergoes a hexagonal-to-tetragonal structural transformation at 24 GPa. The predicted phase equilibrium pressure is much higher than the previously reported pressure range, i.e., 2.5-5.3 GPa, conducted on phase stability of Al{sub 3}BC{sub 3}. A homogeneous orthorhombic shear strain transformation path is proposed for the phase transformation. The transformation enthalpy barrier is estimated to yieldmore » a low value, i.e., 0.129 eV/atom, which ensures that the transformation can readily take place at the predicted pressure. - Graphical abstract: Relative enthalpy of tetragonal phase with respect to hexagonal phase at various pressures. The pressure-induced phase transformation occurs at about 2 and 24 GPa for Mg{sub 3}BN{sub 3} and Al{sub 3}BC{sub 3}, respectively.« less