Giant Pressure-Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin-State Transition in Manganese Chalcogenides

Yonggang Wang; Ligang Bai; Ting Wen; Liuxiang Yang; Huiyang Gou; Yuming Xiao; Paul Chow; Michael Pravica; Wenge Yang; Yusheng Zhao

doi:10.1002/anie.201605410

Giant Pressure-Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin-State Transition in Manganese Chalcogenides

Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10350-3. doi: 10.1002/anie.201605410. Epub 2016 Jul 27.

Authors

Yonggang Wang^{1

2}, Ligang Bai³, Ting Wen⁴, Liuxiang Yang^{5

6}, Huiyang Gou⁶, Yuming Xiao³, Paul Chow³, Michael Pravica⁷, Wenge Yang^{8

9}, Yusheng Zhao^{10

11}

Affiliations

¹ High Pressure Science and Engineering Center, University of Nevada Las Vegas, Las Vegas, NV, 89154, USA. [email protected].
² High Pressure Synergetic Consortium (HPSynC), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA. [email protected].
³ High Pressure Collaborative Access Team (HPCAT), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA.
⁴ Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan, 450006, China.
⁵ High Pressure Synergetic Consortium (HPSynC), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA.
⁶ Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai, 201203, China.
⁷ High Pressure Science and Engineering Center, University of Nevada Las Vegas, Las Vegas, NV, 89154, USA.
⁸ High Pressure Synergetic Consortium (HPSynC), Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA. [email protected].
⁹ Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai, 201203, China. [email protected].
¹⁰ High Pressure Science and Engineering Center, University of Nevada Las Vegas, Las Vegas, NV, 89154, USA. [email protected].
¹¹ Southern University of Science and Technology, Shenzhen, 518055, China. [email protected].

PMID: 27461135
DOI: 10.1002/anie.201605410

Abstract

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.

Keywords: high pressure; intermetallic bonding; lattice collapse; manganese chalcogenides; spin-state transitions.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't