A study of the size dependent blue- and red-shift of the plasmon band of silver nanoparticle films in aqueous solution is reported. A detection scheme, where the particle size is continuously decreased by means of controlled dissolution, while measuring the plasmon band position by UV–vis absorption spectroscopy is used.

Both blue- and red-shifts of the peak position are observed, depending on the presence of electron donors and/or acceptors in the solution, respectively. A great increase in plasmon shifts for smaller particle sizes ( R 10 nm) is demonstrated, which we ascribe to a transition from an extrinsic regime for the larger particles, where shifts of the plasmon frequency are related to changes in the dielectric environment, while the dielectric function of the metal is constant, to an intrinsic regime for the smaller particles. For this intrinsic regime, operative for small particles, nonlocality of the dielectric constant has to be considered. The experimental data are fitted with a recently published theoretical model that takes dynamical surface screening and quantum size effects into account as well as by a Drude model with a corrected effective volume, resulting in a corrected electron density. The reported results have potential for developing nanosensors based on small nanoparticles below 5 nm in size by using their intrinsic response to adsorbed analytes.

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This detection scheme suggests a potential increase in the sensitivity of up to 3×, particularly when redox processes play a role, such as for the detection of reactive oxygen species. Data that relate the particle radii to the nominal deposited thickness; transmission electron microscope images of the AgNP film provided for obtaining the size distrubition; size corrected Drude model that relates the free electron density to an effective volume of the electron gas described in detail; an experiment where the solvent is changed from H 2O 2 to DI water; calculation and discussion of the influence of damping on the extinction peak size. This material is available free of charge via the Internet at. • Ca' Foscari University of Venice • Cagliari State University • Free University of Bolzano • Politecnico di Bari • Scuola Superiore Sant'Anna • University of Bologna • University of Camerino • University of Genoa • University of Messina • University of Naples Federico II • University of Padova • University of Palermo • University of Parma • University of Pavia • University of Perugia • University of Pisa • University of Roma TRE • University of Rome Tor Vergata • University of Salerno • University of Siena • University of Verona.

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