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Journal of Chemical Theory and Computation
Article . 2017 . Peer-reviewed
Data sources: Crossref
https://dx.doi.org/10.48550/ar...
Article . 2017
License: arXiv Non-Exclusive Distribution
Data sources: Datacite
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Kohn–Sham Decomposition in Real-Time Time-Dependent Density-Functional Theory: An Efficient Tool for Analyzing Plasmonic Excitations

Authors: Rossi, Tuomas P.; Kuisma, Mikael; Puska, Martti J.; Nieminen, Risto M.; Erhart; Paul;

Kohn–Sham Decomposition in Real-Time Time-Dependent Density-Functional Theory: An Efficient Tool for Analyzing Plasmonic Excitations

Abstract

The real-time-propagation formulation of time-dependent density-functional theory (RT-TDDFT) is an efficient method for modeling the optical response of molecules and nanoparticles. Compared to the widely adopted linear-response TDDFT approaches based on, e.g., the Casida equations, RT-TDDFT appears, however, lacking efficient analysis methods. This applies in particular to a decomposition of the response in the basis of the underlying single-electron states. In this work, we overcome this limitation by developing an analysis method for obtaining the Kohn-Sham electron-hole decomposition in RT-TDDFT. We demonstrate the equivalence between the developed method and the Casida approach by a benchmark on small benzene derivatives. Then, we use the method for analyzing the plasmonic response of icosahedral silver nanoparticles up to Ag$_{561}$. Based on the analysis, we conclude that in small nanoparticles individual single-electron transitions can split the plasmon into multiple resonances due to strong single-electron-plasmon coupling whereas in larger nanoparticles a distinct plasmon resonance is formed.

11 pages, 3 figures

Country
Finland
Keywords

plasmonic excitations, Chemical Physics (physics.chem-ph), Condensed Matter - Materials Science, Kohn-Sham decomposition, ta114, Condensed Matter - Mesoscale and Nanoscale Physics, tiheysfunktionaaliteoria, ta221, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, plasmonit, Nanoscience Center, Physics - Chemical Physics, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), nanohiukkaset, ta116

  • BIP!
    Impact byBIP!
    citations
    This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
    131
    popularity
    This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
    Top 1%
    influence
    This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
    Top 10%
    impulse
    This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
    Top 1%
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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
131
Top 1%
Top 10%
Top 1%
Green
bronze