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Title: Partial Ionic Character beyond the Pauling Paradigm: Metal Nanoparticles

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp511055k· OSTI ID:1252062
 [1];  [1]
  1. Department of Chemistry, Chemical Theory Center, Inorganometallic Catalyst Design Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States
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A canonical perspective on the chemical bond is the Pauling paradigm: a bond in a molecule containing only identical atoms has no ionic character. However, we show that homonuclear silver clusters have very uneven charge distributions (for example, the C2v structure of Ag4 has a larger dipole moment than formaldehyde or acetone), and we show how to predict the charge distribution from coordination numbers and Hirshfeld charges. The new charge model is validated against Kohn–Sham calculations of dipole moments with four approximations for the exchange–correlation functional. We report Kohn–Sham studies of the binding energies of CO on silver monomer and silver clusters containing 2–18 atoms. We also find that an accurate charge model is essential for understanding the site dependence of binding. In particular we find that atoms with more positive charges tend to have higher binding energies, which can be used for guidance in catalyst modeling and design. Furthermore, the nonuniform charge distribution of silver clusters predisposes the site preference of binding of carbon monoxide, and we conclude that nonuniform charge distributions are an important property for understanding binding of metal nanoparticles in general.

Research Organization:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
Grant/Contract Number:
SC0012702
OSTI ID:
1252062
Alternate ID(s):
OSTI ID: 1384823
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Vol. 118 Journal Issue: 48; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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