Collective Response in DNA-Stabilized Silver Cluster Assemblies from First-Principles Simulations

Abstract

We investigate fluorescence resonant energy transfer and concurrent electron dynamics in a pair of DNA-stabilized silver clusters. For this purpose we introduce a methodology for the simulation of collective opto-electronic properties of coupled molecular aggregates starting from first-principles quantum chemistry, which can be further applied to a broad range of coupled molecular systems to study their electrooptical response. Our simulations reveal the existence of a low-energy coupled excitonic states, which enable ultrafast energy transport between subunits, and give an insight into the origin of the fluorescence signal in coupled DNA-stabilized silver clusters, that have been recently experimentally detected. Hence we demonstrate the possibility to construct an ultra-small energy transmission lines and optical converters based on these hybrid molecular systems.

Structure and luminescence of DNA-templated silver clusters

“…We have primarily reviewed compositional and structural studies of Ag N -DNAs which are synthesized by chemical reduction and, notably, are stable under HPLC purication to enable accurate characterization. Smaller Ag 2 and Ag 3 clusters intercalated between base pairs of dsDNA can be synthesized by electrochemical means and exhibit $300 nm uorescence emission, [177][178][179][180] which supports smaller size and/or different cluster geometry than the HPLC-puried Ag N -DNAs discussed here. The versatility of macromolecular cluster ligands like DNA may permit multiple classes of metal clusters of the same metal species, even for Ag N -DNAs synthesized by chemical reduction.…”

The Role of Molecular Arrangement on the Dispersion in Strongly Coupled Metal-Organic Hybrid Structures

“…In order to investigate the excitonic states which arise in ordered F n ZnPc molecular aggregates we employed our previously developed theoretical approach presented in [22][23][24] in details and briefly described in the SI. The intermolecular coupling was described using the transition charge method 25 implemented as described in.…”

The Role of Molecular Arrangement on the Strongly Coupled Exciton–Plasmon Polariton Dispersion in Metal–Organic Hybrid Structures

“…The transition dipole moments are schematically presented in Figure b, and their magnitudes are summarized in the table below the schema. To investigate the excitonic states which arise in ordered F n ZnPc molecular aggregates, we employed our previously developed theoretical approach presented in refs − in detail and briefly described in the Supporting Information. The intermolecular coupling was described by using the transition charge method implemented as described in ref .…”