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

Kohn–Sham Decomposition in Real-Time Time-Dependent Density-Functional Theory: An Efficient Tool for Analyzing Plasmonic Excitations
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
- University of Jyväskylä Finland
- University of Jyväskylä Finland
- Center for NanoScience Germany
- Center for NanoScience Germany
- Aalto University Finland
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
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
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