Plasmon Couplings from Subsystem Time-Dependent Density Functional Theory

Data di pubblicazione: 17 Ago 2021

RivistaFonte dati: OPENALEXTipo OpenAlex: articleAccesso chiuso
Autori: Giulia Giannone, Szymon Śmiga, Stefania D’Agostino, Eduardo Fabiano, Fabio Della Sala

Many applications in plasmonics are related to the coupling between metallic nanoparticles (MNPs) or between an emitter and a MNP. The theoretical analysis of such a coupling is thus of fundamental importance to analyze the plasmonic behavior and to design new systems. While classical methods neglect quantum and spill-out effects, time-dependent density functional theory (TD-DFT) considers all of them and with Kohn-Sham orbitals delocalized over the whole system. Thus, within TD-DFT, no definite separation of the subsystems (the single MNP or the emitter) and their couplings is directly available. This important feature is obtained here using the subsystem formulation of TD-DFT, which has been originally developed in the context of weakly interacting organic molecules. In subsystem TD-DFT, interacting MNPs are treated independently, thus allowing us to compute the plasmon couplings directly from the subsystem TD-DFT transition densities. We show that subsystem TD-DFT, as well as a simplified version of it in which kinetic contributions are neglected, can reproduce the reference TD-DFT calculations for gap distances greater than about 6 Å or even smaller in the case of hybrid plasmonic systems (i.e., molecules interacting with MNPs). We also show that the subsystem TD-DFT can be also used as a tool to analyze the impact of charge-transfer effects.

Fonte
The Journal of Physical Chemistry A
Volume
125
Fascicolo
33
Pagine
7246-7259
Citazioni
9
ID archivio
956fcae0c1ec520ca5c5abcb5a93a397
Riferimenti
Volume: 125 Issue: 33 Pages: 7246-7259