A1 Journal article (refereed)
Cubic aromaticity in ligand-stabilized doped Au superatoms (2021)

López-Estrada, O., Selenius, E., Zuniga-Gutierrez, B., Malola, S., & Häkkinen, H. (2021). Cubic aromaticity in ligand-stabilized doped Au superatoms. Journal of Chemical Physics, 154(20), Article 204303. https://doi.org/10.1063/5.0050127

JYU authors or editors

Lopez Estrada, Omar
Selenius, Elli
Malola, Sami
Häkkinen, Hannu

Publication details

All authors or editors: López-Estrada, Omar; Selenius, Elli; Zuniga-Gutierrez, Bernardo; Malola, Sami; Häkkinen, Hannu

Journal or series: Journal of Chemical Physics

ISSN: 0021-9606

eISSN: 1089-7690

Publication year: 2021

Publication date: 28/05/2021

Volume: 154

Issue number: 20

Article number: 204303

Publisher: American Institute of Physic

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1063/5.0050127

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/76139

Abstract

The magnetic response of valence electrons in doped gold-based [M@Au8L8]q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh3; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal. Among the cubic-like structures, the strongest aromaticity is observed in Pd- and Pt-doped [M@Au8L8]0 clusters. Interestingly, Pd- and Pt-doping increases the aromaticity as compared to a similar all-gold eight-electron system [Au9L8]+1. With the recent implementation of the GIMIC in the deMon2k code, we investigated the aromaticity in the cubic and butterfly-like M@Au8 core structures, doped with a single M atom from periods 5 and 6 of groups IX–XII. Surprisingly, the doping with Pd and Pt in the cubic structure increases the aromaticity compared to the pure Au case not only near the central atom but encompassing the whole metallic core, following the aromatic trend Pd > Pt > Au. These doped (Pd, Pt)@Au8 nanoclusters show a closed shell 1S21P6 superatom electronic structure corresponding to the cubic aromaticity rule 6n + 2.

Keywords: nanoparticles; clusters; gold; doping (semiconductor technology)

Fields of science: