A1 Journal article (refereed)
Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals (2018)

Kaappa, S., Malola, S., & Häkkinen, H. (2018). Point Group Symmetry Analysis of the Electronic Structure of Bare and Protected Metal Nanocrystals. Journal of Physical Chemistry A, 122(43), 8576-8584. https://doi.org/10.1021/acs.jpca.8b07923

JYU authors or editors

Publication details

All authors or editors: Kaappa, Sami; Malola, Sami; Häkkinen, Hannu

Journal or series: Journal of Physical Chemistry A

ISSN: 1089-5639

eISSN: 1520-5215

Publication year: 2018

Volume: 122

Issue number: 43

Pages range: 8576-8584

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.jpca.8b07923

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/60134

Web address where publication is available: https://arxiv.org/abs/1808.01868


The electronic structures of a variety of experimentally identified gold and silver nanoclusters from 20 to 246 atoms, either unprotected or protected by several types of ligands, are characterized by using point group specific symmetry analysis. The delocalized electron states around the HOMO-LUMO energy gap, originating from the metal s-electrons in the cluster core, show symmetry characteristics according to the point group that describes best the atomic arrangement of the core. This indicates strong effects of the lattice structure and overall shape of the metal core to the electronic structure, which cannot be captured by the conventional analysis based on identification of spherical angular momentum shells in the "superatom" model. The symmetry analysis discussed in this paper is free from any restrictions regarding shape or structure of the metal core, and is shown to be superior to the conventional spherical harmonics analysis for any symmetry that is lower than Ih. As an immediate application, we also demonstrate that it is possible to reach considerable savings in computational time by using the symmetry information inside a conventional linear-response calculation for the optical absorption spectrum of the Ag55 cluster anion, without any loss in accuracy of the computed spectrum. Our work demonstrates an efficient way to analyze the electronic structure of nonspherical, but atomically ordered nanocrystals and ligand-protected clusters with nanocrystal metal cores, and it can be viewed as the generalization of the superatom model demonstrated for spherical shapes 10 years ago (Walter, M.; et al. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 9157-9162).

Keywords: nanoparticles

Free keywords: nanocrystals

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Ministry reporting: Yes

Reporting Year: 2018

JUFO rating: 1

Last updated on 2021-09-06 at 18:19