High-pressure anisotropic distortion of Pb3Bi2S6: a pressure-induced, reversible phase transition with migration of chemical bonds
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High-pressure anisotropic distortion of Pb3Bi2S6 : a pressure-induced, reversible phase transition with migration of chemical bonds. / Olsen, Lars Arnskov; Balic Zunic, Tonci; Makovicky, Emil.
I: Inorganic Chemistry, Bind 47, 2008, s. 6756-6762.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - High-pressure anisotropic distortion of Pb3Bi2S6
T2 - a pressure-induced, reversible phase transition with migration of chemical bonds
AU - Olsen, Lars Arnskov
AU - Balic Zunic, Tonci
AU - Makovicky, Emil
PY - 2008
Y1 - 2008
N2 - The compound Pb3Bi2S6 is investigated by X-ray diffraction on single crystals in a diamond-anvil cell between 0.0001 and 10.5 GPa. It undergoes a first-order phase transition at hydrostatic pressure between 3.7 and 4.9 Gpa. The space group symmetry changes from Bbmm to Pbnm, and the unit-cell volume decreases by 4%. The transition is strongly anisotropic, with a contraction along one of the crystal axes by 16% and expansion along another one by 14%. This is a piezoplastic phase transition, a displacive pressure-induced phase transition with systematic shearing of atomic planes and a migration of chemical bonds in the structure. In the case of Pb3Bi2S6 the transition is achieved by the change of the archetypal architecture of the structure-building modules from a PbS-like to SnS-like arrangement and a loss of mirror planes on the contact surfaces of modules. The phase transition is reversible with a preservation of the single crystal, which is a result of the stereochemical influence and migration of the s2 lone electron pairs of PbII and BiIII.
AB - The compound Pb3Bi2S6 is investigated by X-ray diffraction on single crystals in a diamond-anvil cell between 0.0001 and 10.5 GPa. It undergoes a first-order phase transition at hydrostatic pressure between 3.7 and 4.9 Gpa. The space group symmetry changes from Bbmm to Pbnm, and the unit-cell volume decreases by 4%. The transition is strongly anisotropic, with a contraction along one of the crystal axes by 16% and expansion along another one by 14%. This is a piezoplastic phase transition, a displacive pressure-induced phase transition with systematic shearing of atomic planes and a migration of chemical bonds in the structure. In the case of Pb3Bi2S6 the transition is achieved by the change of the archetypal architecture of the structure-building modules from a PbS-like to SnS-like arrangement and a loss of mirror planes on the contact surfaces of modules. The phase transition is reversible with a preservation of the single crystal, which is a result of the stereochemical influence and migration of the s2 lone electron pairs of PbII and BiIII.
KW - Faculty of Science
KW - Pb3Bi2S6
KW - high pressure anisotopic distortion
KW - Pb3Bi2S6
KW - chemical bonds
M3 - Journal article
VL - 47
SP - 6756
EP - 6762
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
ER -
ID: 8415164