Structural Diversity and Electron Confinement in Li4N: Potential for 0-D, 2-D, and 3-D Electrides

Yuta Tsuji, Prasad L.V.K. Dasari, S. F. Elatresh, Roald Hoffmann, N. W. Ashcroft

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

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 Li4N 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 Li3N. The candidate Li4N structures all contain NLin polyhedra, with n = 6-9. They may be classified into three types, depending on their structural dimensionality: NLin extended polyhedral slabs joined by an elemental Li layer (type a), similar structures, but without the Li layer (type b), and three-dimensionally interconnected NLin 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 Li4N) points to potential amorphous character and likely ionic conductivity in the material.

Original languageEnglish
Pages (from-to)14108-14120
Number of pages13
JournalJournal of the American Chemical Society
Volume138
Issue number42
DOIs
Publication statusPublished - Oct 26 2016

Fingerprint

Phonons
Lithium
Electrons
Ionic conductivity
Charge density
Fermi level
Evolutionary algorithms
Electronic properties
Particle swarm optimization (PSO)
Ground state
Phase diagrams
Crystal structure
Liquids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Structural Diversity and Electron Confinement in Li4N : Potential for 0-D, 2-D, and 3-D Electrides. / Tsuji, Yuta; Dasari, Prasad L.V.K.; Elatresh, S. F.; Hoffmann, Roald; Ashcroft, N. W.

In: Journal of the American Chemical Society, Vol. 138, No. 42, 26.10.2016, p. 14108-14120.

Research output: Contribution to journalArticle

Tsuji, Yuta ; Dasari, Prasad L.V.K. ; Elatresh, S. F. ; Hoffmann, Roald ; Ashcroft, N. W. / Structural Diversity and Electron Confinement in Li4N : Potential for 0-D, 2-D, and 3-D Electrides. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 42. pp. 14108-14120.
@article{ce581b742e8741efb9fbfddc524eb474,
title = "Structural Diversity and Electron Confinement in Li4N: Potential for 0-D, 2-D, and 3-D Electrides",
abstract = "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 Li4N 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 Li3N. The candidate Li4N structures all contain NLin polyhedra, with n = 6-9. They may be classified into three types, depending on their structural dimensionality: NLin extended polyhedral slabs joined by an elemental Li layer (type a), similar structures, but without the Li layer (type b), and three-dimensionally interconnected NLin 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 Li4N) points to potential amorphous character and likely ionic conductivity in the material.",
author = "Yuta Tsuji and Dasari, {Prasad L.V.K.} and Elatresh, {S. F.} and Roald Hoffmann and Ashcroft, {N. W.}",
year = "2016",
month = "10",
day = "26",
doi = "10.1021/jacs.6b09067",
language = "English",
volume = "138",
pages = "14108--14120",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "42",

}

TY - JOUR

T1 - Structural Diversity and Electron Confinement in Li4N

T2 - Potential for 0-D, 2-D, and 3-D Electrides

AU - Tsuji, Yuta

AU - Dasari, Prasad L.V.K.

AU - Elatresh, S. F.

AU - Hoffmann, Roald

AU - Ashcroft, N. W.

PY - 2016/10/26

Y1 - 2016/10/26

N2 - 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 Li4N 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 Li3N. The candidate Li4N structures all contain NLin polyhedra, with n = 6-9. They may be classified into three types, depending on their structural dimensionality: NLin extended polyhedral slabs joined by an elemental Li layer (type a), similar structures, but without the Li layer (type b), and three-dimensionally interconnected NLin 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 Li4N) points to potential amorphous character and likely ionic conductivity in the material.

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 Li4N 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 Li3N. The candidate Li4N structures all contain NLin polyhedra, with n = 6-9. They may be classified into three types, depending on their structural dimensionality: NLin extended polyhedral slabs joined by an elemental Li layer (type a), similar structures, but without the Li layer (type b), and three-dimensionally interconnected NLin 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 Li4N) points to potential amorphous character and likely ionic conductivity in the material.

UR - http://www.scopus.com/inward/record.url?scp=84992735655&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84992735655&partnerID=8YFLogxK

U2 - 10.1021/jacs.6b09067

DO - 10.1021/jacs.6b09067

M3 - Article

AN - SCOPUS:84992735655

VL - 138

SP - 14108

EP - 14120

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 42

ER -