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Updated: May 12, 2026
Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Photoinduced dynamics in a molecule metal nanoparticle complex: mean-field approximation versus exact treatment of
Yaroslav Zelinskyy1, Yuan Zhang, Volkhard May
1Institut für Physik, Humboldt-Universität zu Berlin, Newtonstraße 15, D-12489 Berlin, Germany.
Abstract:
Photoexcitation of a molecule placed in the proximity of a metal nanoparticle (MNP) is described theoretically. For a sufficient small spatial extension of the whole system the molecule-MNP coupling is given by the instantaneous Coulomb-interaction. The coupling can also be considered in terms of a local field to which an external field has been transferred due to the presence of the MNP. It is known that such an approach can explain a number of observations. However, it fails to describe molecular excited state quenching. By considering the exact molecule-MNP Coulomb-coupling and a related mean field approximation which directly leads to a local field description we investigate this disappearance of excited state quenching in detail. Laser pulse induced dynamics in the molecule-MNP system are studied and the importance of higher multipole excitations in a spherical MNP is underlined. The equivalence of the mean field approximation with the exact approach when calculating spectra of linear absorption is also demonstrated.
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