Structural Diversity and Electron Confinement in LiN: Potential for 0-D, 2-D, and 3-D Electrides

In pursuit of new lithium-rich phases and potential electrides within the Li–N phase diagram, we explore theoretically the ground-state structures and electronic properties of LiN at P = 1 atm. Crystal structure exploration methods based on particle swarm optimization and evolutionary algorithms led...

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Publicado en:Journal of the American Chemical Society Vol. 138; no. 42; pp. 14108 - 14121
Autores principales: Yuta Tsuji, Dasari, Prasad L. V. K., Elatresh, S. F., Hoffmann, Roald, Ashcroft, N. W.
Formato: Artículo
Publicado: American Chemical Society 10/26/2016
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 10/26/2016
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      pub: American Chemical Society
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        10.1021/jacs.6b09067
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        atl: Structural Diversity and Electron Confinement in LiN: Potential for 0-D, 2-D, and 3-D Electrides
      aug:
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          Yuta Tsuji
          Dasari, Prasad L. V. K.
          Elatresh, S. F.
          Hoffmann, Roald
          Ashcroft, N. W.
        affil:
          Education Center for Global Leaders in Molecular Systems for Devices, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan.
          Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India.
          Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States.
          Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, New York 14853, United States.
      su:
        Lithium nitrides
        Structural analysis (Science)
        Nitrogen compound synthesis
        Azide synthesis
        Electronic band structure
      sug:
        subj:
          Lithium nitrides
          Structural analysis (Science)
          Nitrogen compound synthesis
          Azide synthesis
          Electronic band structure
      ab: In pursuit of new lithium-rich phases and potential electrides within the Li–N phase diagram, we explore theoretically the ground-state structures and electronic properties of LiN at P = 1 atm. Crystal structure exploration methods based on particle swarm optimization and evolutionary algorithms led to 25 distinct structures, including 23 dynamically stable structures, all quite close to each other in energy, but not in detailed structure. Several additional phases were obtained by following the imaginary phonon modes found in low-energy structures, as well as structures constructed to simulate segregation into Li and LiN. The candidate LiN structures all contain NLi polyhedra, with n = 6–9. They may be classified into three types, depending on their structural dimensionality: NLi extended polyhedral slabs joined by an elemental Li layer (type a), similar structures, but without the Li layer (type b), and three-dimensionally interconnected NLi polyhedra without any layering (type c). We investigate the electride nature of these structures using the electron localization function and partial charge density around the Fermi level. All of the structures can be characterized as electrides, but they differ in electronic dimensionality. Type-a and type-b structures may be classified as two-dimensional (2-D) electrides, while type-c structures emerge quite varied, as 0-D, 2-D, or 3-D. The calculated structural variety (as well as detailed models for amorphous and liquid LiN) points to potential amorphous character and likely ionic conductivity in the material.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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