Theory of Optical Coupling Effects Among Surfactant Au Nanoparticles Films

In previous reports, Dalfovo et al. showed experimentally that thin films of Au nanoparticles (NP) with organic coating change their optical properties when exposed to several analytes in the vapor phase (Anal Chem 84:4886–4892 2012; J Phys Chem C 119:5098–5106 2015). This optical behavior was associated with changes in the mean distance between nanoparticles, which resulted in a displacement of their plasmon bands towards blue or red in the presence of toluene (Tol) or ethanol (EtOH) vapors, respectively. In the report by Dalfovo et al. (J Phys Chem C 119:5098–5106 2015), in-situ grazing-incidence small-angle X-ray spectroscopy (GISAXS) was performed to determine changes in the inter-NP distance within the film. In the present work, we perform theoretical calculations to interpret the results obtained by Dalfovo et al. (Anal Chem 84:4886–4892 2012; J Phys Chem C 119:5098–5106 2015). For this purpose, we employ two different theoretical approaches, a quasi-static method (QS) and the Korringa-Kohn-Rostoker method (KKR), in order to describe the plasmon resonance shift as a function of the inter-NP distance changes during exposure to Tol and EtOH vapors. Both theoretical approaches describe qualitatively the behavior observed in previous experimental results that correlate the plasmon resonant wavelength with the inter-NP distance obtained by GISAXS. Our theoretical results show that the plasmon resonant wavelength strongly depends on the ratio between the inter-particle distance and the diameter of the nanoparticles and consequently, these films could be used for optical tuning.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada