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Title: Ab initio investigations of the electronic structure and chemical bonding of Li{sub 2}ZrN{sub 2}

Abstract

The electronic structure of the ternary nitride Li{sub 2}ZrN{sub 2} is examined from ab initio with DFT computations for an assessment of the properties of chemical bonding. The compound is found insulating with 1.8 eV band gap; it becomes metallic and less ionic upon removal of one equivalent of Li. The chemical interaction is found mainly between Zr and N on one hand and Li and N on the other hand. While all pair interactions are bonding, antibonding N-N interactions are found dominant at the top of the valence band of Li{sub 2}ZrN{sub 2} and they become less intense upon removal of Li. From energy differences the partial delithiation leading to Li{sub 2-x}ZrN{sub 2} (x={approx}1) is favored. - Graphical abstract: Trigonal structure of Li{sub 2}ZrN{sub 2} showing the Zr-N-Li layers along the c-axis. Highlights: Black-Right-Pointing-Pointer Li{sub 2}ZrN{sub 2} calculated insulating with a 1.8 eV gap in agreement with its light green color. Black-Right-Pointing-Pointer Lithium de-intercalation is energetically favored for one out of two Li equivalents. Black-Right-Pointing-Pointer Li plays little role in the change of the structure, ensured by Zr and N binding. Black-Right-Pointing-Pointer Similar changes in the electronic structure as for various intercalated phases of ZrN.

Authors:
 [1];  [2];  [3];  [3]
  1. CNRS, Universite de Bordeaux, ICMCB, 87 Avenue du Docteur Albert Schweitzer, 33600 Pessac (France)
  2. Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, D-48149 Muenster (Germany)
  3. Universite Saint Esprit de Kaslik (USEK), Faculte des Sciences, URA GREVE (CNRS/USEK/UL), Jounieh (Lebanon)
Publication Date:
OSTI Identifier:
22012146
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: . 190; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; CHEMICAL BONDS; CRYSTALS; ELECTRONIC STRUCTURE; LAYERS; LITHIUM NITRIDES; PAIRING INTERACTIONS; ZIRCONIUM NITRIDES

Citation Formats

Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr, Poettgen, R., E-mail: pottgen@uni-muenster.de, Al Alam, A.F., E-mail: adelalalam@usek.edu.lb, and Ouaini, N., E-mail: naimouaini@usek.edu.lb. Ab initio investigations of the electronic structure and chemical bonding of Li{sub 2}ZrN{sub 2}. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.02.038.
Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr, Poettgen, R., E-mail: pottgen@uni-muenster.de, Al Alam, A.F., E-mail: adelalalam@usek.edu.lb, & Ouaini, N., E-mail: naimouaini@usek.edu.lb. Ab initio investigations of the electronic structure and chemical bonding of Li{sub 2}ZrN{sub 2}. United States. doi:10.1016/J.JSSC.2012.02.038.
Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr, Poettgen, R., E-mail: pottgen@uni-muenster.de, Al Alam, A.F., E-mail: adelalalam@usek.edu.lb, and Ouaini, N., E-mail: naimouaini@usek.edu.lb. Fri . "Ab initio investigations of the electronic structure and chemical bonding of Li{sub 2}ZrN{sub 2}". United States. doi:10.1016/J.JSSC.2012.02.038.
@article{osti_22012146,
title = {Ab initio investigations of the electronic structure and chemical bonding of Li{sub 2}ZrN{sub 2}},
author = {Matar, S.F., E-mail: matar@icmcb-bordeaux.cnrs.fr and Poettgen, R., E-mail: pottgen@uni-muenster.de and Al Alam, A.F., E-mail: adelalalam@usek.edu.lb and Ouaini, N., E-mail: naimouaini@usek.edu.lb},
abstractNote = {The electronic structure of the ternary nitride Li{sub 2}ZrN{sub 2} is examined from ab initio with DFT computations for an assessment of the properties of chemical bonding. The compound is found insulating with 1.8 eV band gap; it becomes metallic and less ionic upon removal of one equivalent of Li. The chemical interaction is found mainly between Zr and N on one hand and Li and N on the other hand. While all pair interactions are bonding, antibonding N-N interactions are found dominant at the top of the valence band of Li{sub 2}ZrN{sub 2} and they become less intense upon removal of Li. From energy differences the partial delithiation leading to Li{sub 2-x}ZrN{sub 2} (x={approx}1) is favored. - Graphical abstract: Trigonal structure of Li{sub 2}ZrN{sub 2} showing the Zr-N-Li layers along the c-axis. Highlights: Black-Right-Pointing-Pointer Li{sub 2}ZrN{sub 2} calculated insulating with a 1.8 eV gap in agreement with its light green color. Black-Right-Pointing-Pointer Lithium de-intercalation is energetically favored for one out of two Li equivalents. Black-Right-Pointing-Pointer Li plays little role in the change of the structure, ensured by Zr and N binding. Black-Right-Pointing-Pointer Similar changes in the electronic structure as for various intercalated phases of ZrN.},
doi = {10.1016/J.JSSC.2012.02.038},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = . 190,
place = {United States},
year = {2012},
month = {6}
}