Plasmonic systems, such as metal nanoparticles, are becoming increasingly important in spectroscopies and devices because of their ability to enhance, even by several orders of magnitude, the photophysical properties of neighbouring systems. In particular, it has been shown both theoretically and experimentally that combining nanoplasmonic devices with natural light-harvesting proteins substantially increases the fluorescence and absorption properties of the system. This kind of biohybrid device can have important applications in the characterization and design of efficient light-harvesting systems. In the present work, the FMO light-harvesting protein was combined with gold nanoparticles of different sizes, and its photophysical properties were characterized using a multiscale quantum-mechanical classical-polarizable and continuum model (QM/MMPol/PCM). By optimal tuning of the plasmon resonance of the metal nanoparticles, fluorescence enhancements of up to 2 orders of magnitude were observed. Orientation effects were found to be crucial: amplifications by factors of up to 300 were observed for the absorption process, while the radiative decay of the emitting state increased at most by a factor of 10, mostly as a result of poor alignment of the emitting state with the considered metal aggregates. Despite being a limiting factor for high-fluorescence-enhancement devices, the strong orientation dependence may represent an important feature of the natural light-harvesting system that could allow selective enhancement of a specific excited state of the complex.
|Autori:||Oliviero Andreussi;Stefano Caprasecca;Lorenzo Cupellini;Ingrid Guarnetti-Prandi;Ciro A. Guido;Sandro Jurinovich;Lucas Viani;Benedetta Mennucci|
|Titolo:||Plasmon Enhanced Light Harvesting: Multiscale Modeling of the FMO Protein Coupled with Gold Nanoparticles|
|Anno del prodotto:||2014|
|Digital Object Identifier (DOI):||10.1021/jp509870b|
|Appare nelle tipologie:||1.1 Articolo in rivista|