Surface-Enhanced Raman Scattering (SERS) of Nitrothiophenol Isomers Chemisorbed on TiO2

Surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculations were used to investigate the nature of the charge-transfer (CT) process between nitrothiophenol (NTP) isomers and the n-type semiconductor, TiO₂. The Raman signals of p-NTP and m-NTP that were chemisorbed onto TiO₂ were significantly enhanced with respect to their corresponding neat compounds. In particular, an enhancement factor (EF) of 10²–10³ was observed for both p-NTP and m-NTP, with m-NTP displaying a larger EF compared to p-NTP. The Raman signal of o-NTP on TiO₂ was not detectable, owing to interference from fluorescence emissions. A molecule-to-TiO₂ charge-transfer mechanism was responsible for the enhanced Raman signals observed in p-NTP and m-NTP. This transfer was due to a strong coupling between the adsorbate and the metal oxide, which led to an optically driven CT transition from the HOMO of NTP into the conduction band of TiO₂. Based on the mesomeric effect, the NO₂ group para to the thiol had a stronger electron-withdrawing ability than the NO₂ group at the meta position. A less-efficient CT transition from p-NTP to TiO₂ in the surface complex resulted in a weaker Raman-signal enhancement for p-NTP compared to m-NTP. The DFT calculation determined that the HOMO and the LUMO of NTP bound to TiO₂ were located entirely on the adsorbate and the semiconductor, respectively, thereby supporting the experimental findings that a molecule-to-TiO₂ mechanism was the driving force behind the observed SERS effect.     

Local Modulation of the Redox State of p‐Nitrothiophenol Self‐Assembled Monolayers Using the Direct Mode of Scanning Electrochemical Microscopy

Local redox conversion of nitro end groups of a 4‐nitrothiophenol self‐assembled monolayer on gold is achieved by direct‐mode scanning electrochemical microscopy (SECM). Potential pulses are applied to the modified gold surface leading to local reduction of nitro end groups to either hydroxylamine (?0.47 V, see picture) or amino groups (?0.6 V) exclusively beneath the positioned SECM tip.

     

Distinguishing chemical and electromagnetic enhancement in surface‐enhanced Raman spectra: The case of para‐nitrothiophenol

Surface‐enhanced Raman spectra are simulated using a combined classical electrodynamics/real‐time time‐dependent density functional theory approach and compared to experiments. Emphasis is put on discerning between chemical and electromagnetic enhancement. Therefore, three different calculation scenarios are investigated using para‐nitrothiophenol as a test molecule. In the first one, corresponding to electromagnetic enhancement, we simulate the molecule alone with ab initio computations incorporating the electromagnetic field emitted by a nanoparticle. Chemical enhancement is modeled in the second scenario, where we include not only the molecule into the quantum chemistry calculations but also metal atoms of the nanoparticle. Here, any modification of the electromagnetic field due to the nanoparticle is not considered. In the third scenario, the former two setups are combined and demanding simulations of the hybrid system containing the molecule and the metal atoms exposed to a strongly modified electromagnetic field due to the plasmonic properties of the metallic nanoparticles are considered. Results are compared to our experimentally measured spectra. Based on our analysis, we show here on rigorous grounds that the electromagnetic effect leads to increased absolute Raman scattering cross sections but no change of the relative intensities. In contrast, the chemical effect leads to changes in relative peak height and also to newly emerging bands in the spectrum. These findings will have major implications in any study that concerns the interaction of molecules with metallic nanostructures. Copyright © 2013 John Wiley & Sons, Ltd.