Analytical Approaches To Identify Plasmon-like Excited States in Bare and Ligand-Protected Metal Nanoclusters

Gieseking, Rebecca L.  M.; Ashwell, Adam P.; Ratner, Mark A.; Schatz, George C.

doi:10.1021/acs.jpcc.9b10569

Title: Analytical Approaches To Identify Plasmon-like Excited States in Bare and Ligand-Protected Metal Nanoclusters

Journal Article · Wed Jan 15 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.9b10569· OSTI ID:1598588

^[1]; Ashwell, Adam P. ^[2];

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Brandeis Univ., Waltham, MA (United States)
Northwestern Univ., Evanston, IL (United States)

Noble metal nanoclusters containing dozens to hundreds of metal atoms are of great interest because of their unique optical properties. Classical electrodynamics fails to describe the optical properties of clusters smaller than ~5 nm, so quantum mechanical models are needed to describe these clusters. However, it is challenging to identify which features of the computed excited states indicate plasmon-like character, particularly in a way that is generalizable to the ligand-protected clusters that are commonly studied in experiments. We present an analytical method to identify plasmon-like excited states using three quantifiable indicators that must be considered in combination: (1) large superatomic character, (2) large collectivity among single-particle excitations, and (3) large additivity of contributions of these single-particle excitations to the transition dipole moment. Visualizing these three indicators on a single plot enables rapid classification of hundreds of excited states into plasmon-like, collective, single-particle, or interband categories, or as intermediate between these categories. Lastly, this method is used to identify excited states with plasmon-like character in both bare and ligand-protected Ag clusters at the TDDFT level. Using these three nearly orthogonal indicators in combination provides more information than any one criterion can provide.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0004752

OSTI ID:: 1598588

Journal Information:: Journal of Physical Chemistry. C, Vol. 124, Issue 5; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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Plasmon excitations in chemically heterogeneous nanoarrays Conley, Kevin; Nayyar, Neha; Rossi, Tuomas P. Physical Review B, Vol. 101, Issue 23 https://doi.org/10.1103/physrevb.101.235132	journal	June 2020

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