Application of the Condensed Fukui Function to Predict Reactivity in Core–Shell Transition Metal Nanoparticles

Journal Article · Mon Jul 01 04:00:00 EDT 2013 · Electrochimica Acta

DOI:https://doi.org/10.1016/j.electacta.2012.12.072· OSTI ID:1233791

Allison, Thomas C.; Tong, Yu ye J.

Chemical reactivity descriptors are a powerful means for understanding reactivity in a wide variety of chemical compounds. These descriptors, rooted in density functional theory, have found broad application in organic chemical reactions, but have not been as widely applied for other classes of chemical species such as nanoparticles, which are the subject of this article. Specifically, we explore application of the Fukui function, the global hardness and softness, the local softness, and the dual descriptor to pure metallic and core–shell nanoparticles, with and without a CO molecule bound to the surface. We find that the Fukui function is useful in predicting and interpreting chemical reactivity, and that it correlates well with the results of the popular d-band center method. Differences in the Fukui function before and after bonding of a CO molecule to the surface of a nanoparticle reveal interesting information about the reactivity of the nanoparticle surface. The change in the Fukui function when an electric field is applied to the molecule is also considered. Though the results are generally good, some of the limitations of this approach become clear.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1233791
• Journal Information: Electrochimica Acta, Journal Name: Electrochimica Acta Vol. 101; ISSN 0013-4686
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

Chemical reactivity theory
Environmental Molecular Sciences Laboratory
Fukui function
Nanoparticles