First-principles spectra of Au nanoparticles: from quantum to classical absorption

Samuel Hernandez, Yantao Xia, Vojtěch Vlček*, Robert Boutelle, Roi Baer, Eran Rabani, Daniel Neuhauser

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


Absorption cross-section spectra for gold nanoparticles were calculated using fully quantum Stochastic Density Functional Theory and a classical Finite-Difference Time Domain Maxwell solver. Spectral shifts were monitored as a function of size (1.3– (1.3–3.1 nm) and shape (octahedron, cubeoctahedron and truncated cube). Even though the classical approach is forced to fit the quantum time-dependent density functional theory at 3.1 nm, at smaller sizes there is a significant deviation as the classical theory is unable to account for peak splitting and spectral blueshifts even after quantum spectral corrections. We attribute the failure of classical methods at predicting these features to quantum effects and low density of states in small nanoparticles. Classically, plasmon resonances are modelled as collective conduction electron excitations, but at small nanoparticle size these excitations transition to few or even individual conductive electron excitations, as indicated by our results.

Original languageAmerican English
Pages (from-to)2506-2511
Number of pages6
JournalMolecular Physics
Issue number19-20
StatePublished - 18 Oct 2018

Bibliographical note

Publisher Copyright:
© 2018, © 2018 Informa UK Limited, trading as Taylor & Francis Group.


  • Time-dependent density functional theory
  • optical spectra
  • plasmons
  • stochastic methods and algorithms


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