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Lone electron pair (E) role on the crystal structures and the mechanism of high ionic conductivity of PbSnF4E2. Stereochemical and ab initio investigations
Institution:1. CNRS, ICMCB, University of Bordeaux, 33600 Pessac, France;2. CNRS, LCTS, University of Bordeaux, 33600 Pessac, France;1. Institute of High-Temperature Electrochemistry, UB RAS, 20 Academicheskaya Str., 620137 Yekaterinburg, Russia;2. Institute of Solid State Chemistry, UB RAS, 91 Pervomayskaya Str., 620990 Yekaterinburg, Russia;3. Ural Federal University Named after the First President of Russia B.N. Yeltsin, 19 Mira Str., 620002, Yekaterinburg, Russia;1. Department of Physics, Bangalore University, Jnanabharathi Campus, Bengaluru, 560056, India;2. New Chemistry Unit, Jawaharlal Nehru Center for Advanced Scientific Research, Jakkur P. O., Bangalore, 560064, India;3. UGC-DAE-Consortium for Scientific Research, Mumbai Centre, BARC Campus, Mumbai, 400085, India;1. School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China;2. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun 130022, China
Abstract:The F anion mobility of archetype fast ionic conductor PbSnF4 formerly investigated by neutron diffraction with temperature is revisited based on a joint stereochemical and DFT investigation. It is mainly shown that a rapid exchange between F anions at the different tetragonal lattice sites is enhanced within the polyhedra enclosing the lone pair E in a dynamic change of coordination from octahedral to square pyramidal as for Sn(II). E stereoactivity in the interspaces along c direction is illustrated by the electron localization function ELF isosurface representations and followed by the non linear change of the c lattice constant with temperature.
Keywords:Ionic conductivity  Electron lone pair  DFT  ELF
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