Partial ionic character beyond the pauling paradigm: Metal nanoparticles

Kaining Duanmu, Donald G. Truhlar

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

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. Thus, 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.

Original languageEnglish (US)
Pages (from-to)28069-28074
Number of pages6
JournalJournal of Physical Chemistry C
Volume118
Issue number48
DOIs
StatePublished - Dec 4 2014

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Metal nanoparticles
Charge distribution
Silver
charge distribution
silver
nanoparticles
Dipole moment
Carbon Monoxide
Binding energy
Atoms
metals
dipole moments
binding energy
Binding Sites
atoms
Chemical bonds
chemical bonds
Acetone
formaldehyde
coordination number

Cite this

Partial ionic character beyond the pauling paradigm : Metal nanoparticles. / Duanmu, Kaining; Truhlar, Donald G.

In: Journal of Physical Chemistry C, Vol. 118, No. 48, 04.12.2014, p. 28069-28074.

Research output: Contribution to journalArticle

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