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  • Title: High-temperature crystal structures and chemical modifications in RbH(2)PO(4).
    Author: Botez CE, Martinez H, Tackett RJ, Chianelli RR, Zhang J, Zhao Y.
    Journal: J Phys Condens Matter; 2009 Aug 12; 21(32):325401. PubMed ID: 21693965.
    Abstract:
    We have used laboratory and synchrotron x-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline RbH(2)PO(4) upon heating within the 30-250 °C temperature interval. Our data show no evidence of the previously reported onset of partial polymerization at T = 96 °C (Park et al 2001 J. Phys.: Condens. Matter 13 9411) which was proposed as an explanation for the high-temperature proton conductivity enhancement in phosphate-based solid acids. Instead, we found that a tetragonal [Formula: see text] monoclinic polymorphic transition initiates at T≈90 °C. The transition is complete at T≈130 °C, and the new monoclinic RbH(2)PO(4) polymorph is stable upon further heating to T = 200 °C. Moreover, its crystal structure is isomorphic to that of monoclinic CsH(2)PO(4). This remarkable similarity suggests that the microscopic structures and dynamics responsible for the high-temperature superprotonic behavior of RbH(2)PO(4) could be the same as those of its Cs-based counterpart.
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