Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters
Abstract
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 pointsmore »
- Authors:
-
- Virginia Commonwealth Univ., Richmond, VA (United States). Dept. of Physics
- Publication Date:
- Research Org.:
- Virginia Commonwealth Univ., Richmond, VA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1474038
- Alternate Identifier(s):
- OSTI ID: 1361925
- Grant/Contract Number:
- SC0006420
- Resource 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)
- 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
Citation Formats
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., 2017.
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. https://doi.org/10.1063/1.4985093
Grover, Cameron J., Reber, Arthur C., and Khanna, Shiv N. Thu .
"Ionic versus metallic bonding in AlnNam and AlnMgm (m ≤ 3, n + m ≤ 15) clusters". United States. https://doi.org/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 = {Thu Jun 08 00:00:00 EDT 2017},
month = {Thu Jun 08 00:00:00 EDT 2017}
}
Web of Science
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