• Katrusiak, Andrzej
• Dziubek, Kamil F.
• Hanfland, Michael
• Zachara, Janusz
• Guńka, Piotr A.
• Dranka, Maciej

Abstract

Claudetite II, one of the three known As2O3 polymorphs, has been studied by single-crystal synchrotron X-ray diffraction up to 21 GPa. Three new As2O3 polymorphs, all structurally related to claudetite II, are formed through a sequence of single-crystal-to-single-crystal phase transitions: the ambient pressure claudetite IIα (monoclinic space group P21/n, Z = 4) transforms at 2 GPa continuously to phase IIα′ (P21/a, Z = 8), at 6 GPa to phase IIα″ (P21/a, Z = 24), and at 11 GPa it transforms discontinuously to phase IIβ (P21, Z = 4). The experimentally observed phases α–α″ are centrosymmetric, whereas phase β is polar. A significant hysteresis on decompression skips the α″ phase and only α′ phase is formed before the ambient pressure α polymorph is recovered. The transitions and compression of claudetite II preserve its structure of 2D polymeric As2O3 layers; however, the intersheet As···As distances are compressed at 21 GPa to about 2.9 Å, only 0.5 Å more than the As–As single bond length. Previous DFT modeling of claudetite II structure under pressure suggested only one transformation around 15 GPa, but to a different structure (Guńka, P. A.; Dranka, M.; Piechota, J.; Żukowska, G. Z.; Zalewska, A.; Zachara, J. Cryst. Growth Des. 2012, 5663).

Topics

• impedance spectroscopy
• phase
• x-ray diffraction
• phase transition
• density functional theory
• space group
• Arsenic