Partial Ionic Character beyond the Pauling Paradigm: Metal Nanoparticles

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• 作者：Kaining Duanmu ; Donald G. Truhlar
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：December 4, 2014
• 年：2014
• 卷：118
• 期：48
• 页码：28069-28074
• 全文大小：251K
• ISSN：1932-7455

文摘

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 C_2v 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鈥揝ham calculations of dipole moments with four approximations for the exchange鈥揷orrelation functional. We report Kohn鈥揝ham studies of the binding energies of CO on silver monomer and silver clusters containing 2鈥?8 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.