Crystal Structure Relation between Tetragonal and Orthorhombic CsAlD4: DFT and Time-of-Flight Neutron Powder Diffraction Studies

Date

2015

Authors

Bernert, Thomas
Krech, Daniel
Kockelmann, Winfried
Felderhoff, Michael
Frankcombe, Terry
Weidenthaler, Claudia

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Wiley-VCH Verlag GMBH

Abstract

The crystal structures of orthorhombic and tetragonal CsAlD4 were refined from time-of-flight neutron powder diffraction data starting from atomic positions predicted from DFT calculations. The earlier proposed crystal structure of orthorhombic CsAlH4 is confirmed. For tetragonal CsAlH4, DFT calculations predicted a crystal structure in I41/amd as potential minimum structure, while from neutron diffraction studies of CsAlD4 best refinement is obtained for a disordered structure in the space group I41/a, with a = 5.67231(9) Å, c = 14.2823(5) Å. While the caesium atoms are located on the Wyckoff position 4b and aluminium at Wyckoff position 4a, there are two distinct deuterium positions at the Wyckoff position 16f with occupancies of 50 % each. From this structure, the previously reported phase transition between the orthorhombic and tetragonal polymorphs could be explained.

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Source

European Journal of Inorganic Chemistry

Type

Journal article

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Restricted until

2037-12-31