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Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods

TitleClassical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods
Publication TypeJournal Article
Year of Publication2017
AuthorsSinha-Roy, R., Garcia-Gonzalez P., Weissker H. - C., Rabilloud F., & Fernandez-Dominguez A. I.
Keywordsab initio methods; atomic chain; classical optics; d-electron excitations; localized plasmon resonance; nanorod; time-dependent density functional theory

Applications of noble metal clusters and nanoparticles in different size ranges abound, from a couple of atoms through mesoscopic sizes. Classical electromagnetics calculations are now employed on smaller and smaller sizes, creating an effervescent dynamic in fields such as plasmonics and approaching the tiny sizes where quantum effects and the atomistic structure of matter play predominant roles. Nonetheless, explicit demonstrations of their merits and limitations are rare. Here we study the optical absorption of subnanometric elongated coinage -metal particles using ab initio and classical electromagnetics methods. The comparison between both approaches reveals that the classical plasmonic frequencies are in astonishing agreement with those predicted by ab initio theory for atomistic three-dimensional rods and quasi -one-dimensional chains, as long as collective surface-plasmon resonances lie far below the onset of d-electron excitations. The physical origin of this striking agreement is clarified through the analysis of the resonant induced electron densities and with the aid of model calculations for a purely one-dimensional system of electrons. Furthermore, we show that even when plasmonic/collective and electron hole excitations are strongly coupled, the classical description accounts rather well for the spectral average of the corresponding quantum hybrid excitations. Our theoretical findings demonstrate that classical optics is surprisingly accurate in describing localized surface plasmon resonances even for angstrom-sized systems, provided the geometrical modeling of the atomistic structures is properly defined.

Date PublishedJUN
Type of ArticleArticle
Citation Key ISI:000404098200027