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Title: Ionic versus metallic bonding in Al nNa m and Al nMg m (m ≤ 3, n + m ≤ 15) clusters

First principles electronic structure studies on the ground state geometries, stability, and the electronic structure of Al nNa m and Al nMg m (m ≤ 3, n + m ≤ 15) clusters have been carried out to examine the nature of bonding between Na or Mg and Al. Identifying whether the bonding is ionic or metallic in bulk materials is typically straightforward; however, in small clusters where quantum confinement is important, the nature of bonding may become unclear. Here, we have performed a critical analysis of the bonding in these bimetallic clusters using charge analysis, electrical dipole moments, hybridization of the atomic orbitals, the Laplacian of the charge density at the bond critical points, and the change in the bonding energy between neutral and anionic forms of the cluster. For Na nAl m clusters, we find that the Na binding is primarily ionic, while the bonding in Al nMg m is primarily metallic. We find that the Mulliken population of the 3 p orbital of Na and Mg can provide a rapid assessment of the nature of bonding. We also find that the Hirshfeld charge and dipole moments are effective indicators, when placed in context. We found that the Laplacianmore » of the charge density at the bond critical points can be misleading in identifying whether the bonding is ionic or metallic in small clusters.« less
Authors:
 [1] ; ORCiD logo [1] ;  [1]
  1. Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
Publication Date:
Grant/Contract Number:
SC0006420
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Virginia Commonwealth Univ., Richmond, VA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; chemical compounds and components; chemical bonding; operator theory; quantum confinement; chemical elements; electronic shell; HOMO-LUMO gap; ions and properties; electrostatics; electric dipole moments
OSTI Identifier:
1474038
Alternate Identifier(s):
OSTI ID: 1361925

Grover, Cameron J., Reber, Arthur C., and Khanna, Shiv N.. Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters. United States: N. p., Web. doi:10.1063/1.4985093.
Grover, Cameron J., Reber, Arthur C., & Khanna, Shiv N.. Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters. United States. doi:10.1063/1.4985093.
Grover, Cameron J., Reber, Arthur C., and Khanna, Shiv N.. 2017. "Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters". United States. doi:10.1063/1.4985093. https://www.osti.gov/servlets/purl/1474038.
@article{osti_1474038,
title = {Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters},
author = {Grover, Cameron J. and Reber, Arthur C. and Khanna, Shiv N.},
abstractNote = {First principles electronic structure studies on the ground state geometries, stability, and the electronic structure of AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters have been carried out to examine the nature of bonding between Na or Mg and Al. Identifying whether the bonding is ionic or metallic in bulk materials is typically straightforward; however, in small clusters where quantum confinement is important, the nature of bonding may become unclear. Here, we have performed a critical analysis of the bonding in these bimetallic clusters using charge analysis, electrical dipole moments, hybridization of the atomic orbitals, the Laplacian of the charge density at the bond critical points, and the change in the bonding energy between neutral and anionic forms of the cluster. For NanAlm clusters, we find that the Na binding is primarily ionic, while the bonding in AlnMgm is primarily metallic. We find that the Mulliken population of the 3p orbital of Na and Mg can provide a rapid assessment of the nature of bonding. We also find that the Hirshfeld charge and dipole moments are effective indicators, when placed in context. We found that the Laplacian of the charge density at the bond critical points can be misleading in identifying whether the bonding is ionic or metallic in small clusters.},
doi = {10.1063/1.4985093},
journal = {Journal of Chemical Physics},
number = 22,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

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