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Giant Pressure‐Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin‐State Transition in Manganese Chalcogenides
Author(s) -
Wang Yonggang,
Bai Ligang,
Wen Ting,
Yang Liuxiang,
Gou Huiyang,
Xiao Yuming,
Chow Paul,
Pravica Michael,
Yang Wenge,
Zhao Yusheng
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201605410
Subject(s) - intermetallic , metastability , condensed matter physics , phase transition , manganese , transition metal , lattice (music) , materials science , spin states , spin transition , chemical physics , chemistry , crystallography , physics , metallurgy , biochemistry , organic chemistry , alloy , acoustics , catalysis
Materials with an abrupt volume collapse of more than 20 % during a pressure‐induced phase transition are rarely reported. In such an intriguing phenomenon, the lattice may be coupled with dramatic changes of orbital and/or the spin‐state of the transition metal. A combined in situ crystallography and electron spin‐state study to probe the mechanism of the pressure‐driven lattice collapse in MnS and MnSe is presented. Both materials exhibit a rocksalt‐to‐MnP phase transition under compression with ca. 22 % unit‐cell volume changes, which was found to be coupled with the Mn 2+ (d 5 ) spin‐state transition from S =5/2 to S =1/2 and the formation of Mn−Mn intermetallic bonds as supported by the metallic transport behavior of their high‐pressure phases. Our results reveal the mutual relationship between pressure‐driven lattice collapse and the orbital/spin‐state of Mn 2+ in manganese chalcogenides and also provide deeper insights toward the exploration of new metastable phases with exceptional functionalities.