Surface control in the adsorption of tebuthiuron on modified silver surfaces tracked by surface-enhanced Raman...

The vibrational assignment of the Raman and surface-enhanced Raman scattering (SERS) spectra of the herbicide tebuthiuron (TBH) was accomplished, which allowed unprecedented propositions for adsorption geometries on the surface of silver nanoparticles (AgNP). Ascribed SERS features allowed suggesting that the adsorption occurred through nitrogen atoms of thiadiazole group, since intense band shift assigned to ring mode was marking of the coordination with the metallic surface. AgNP were treated with different surface modifiers that leaded to substantial changes in TBH adsorption geometries. Spectral changes, as the enhancement of out-of-plane ring modes, were indicative of the presence of tilted thiadiazole geometries in relation to the silver surface. Density Functional Theory (DFT) calculations from TBH molecules, in isolation and in interaction with ten-atom cluster of silver leaded to obtain theoretical spectra that gave support to interpret experimental Raman and SERS spectra.