Structural Diversity and Electron Confinement in Li 4 N: Potential for 0-D, 2-D, and 3-D Electrides

• Published in: Journal of the American Chemical Society Vol. 138; no. 42; pp. 14108 - 14120
• Main Authors: Tsuji, Yuta, Dasari, Prasad L V K, Elatresh, S F, Hoffmann, Roald, Ashcroft, N W
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society (ACS) 26.10.2016
• Subjects: catalysis (heterogeneous), solar (photovoltaic), phonons, thermoelectric, energy storage (including batteries and capacitors), hydrogen and fuel cells, superconductivity, charge transport, mesostructured materials, materials and chemistry by design, synthesis (novel materials)
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b09067

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 Li N 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 Li N. The candidate Li N 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 Li N) points to potential amorphous character and likely ionic conductivity in the material.