We wish to show that gas-phase studies of small metal cluster-biomolecule complexes provide fundamental insights into the mechanism leading to enhanced optical absorption in nanoparticle-biomolecular hybrid systems. Here we present, for the first time, a joint experimental and theoretical study of photoabsorption and photofragmentation of the silver trimer-tryptophan cation complex ([Trp center dot Ag-3](+)). We demonstrate that binding the metal cluster to a biomolecule leads to a remarkably high optical absorption as compared to the bare tryptophan or the [Trp center dot Ag](+) complex. As calculations show this arises due to coupling between the excitations in the metallic subunit with a charge transfer excitation to the tryptophan molecule. (c) 2006 American Institute of Physics.
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