Search for: All records

Surface-enhanced Raman scattering (SERS) provides orders of magnitude of enhancements to weak Raman scattering. The improved sensitivity and chemical information conveyed in the spectral signatures make SERS a valuable analysis technique. Most of SERS enhancements come from the electromagnetic enhancement mechanism, and changes in spectral signatures are usually attributed to the chemical enhancement mechanism. As the electromagnetic mechanism has been well studied, we will give an overview of models related to the chemical mechanism, which explain the Raman response in terms of electronic transitions or induced electron densities. In the first class of models based on electronic transitions, chemical enhancements are attributed to changes in transitions of the molecule and new charge transfer transitions. The second class of models relate chemical enhancements to charge flows near the molecule–metal interface by partitioning the induced electron density of the SERS system in real space. Selected examples will be given to illustrate the two classes of models, and connections between the models are demonstrated for prototypical SERS systems. 

The exceptional stability of N-heterocyclic carbene (NHC) monolayers on gold surfaces and nanoparticles (AuNPs) is enabling new and diverse applications from catalysis to biomedicine. Our understanding of NHC reactivity at surfaces; however, is quite nascent when compared to the long and rich history of NHC ligands in organometallic chemistry. In this work, well-established transmetalation reactions, previously developed for NHC transfer in homogeneous organometallic systems, are explored to determine how they can be used to create carbene functionalized gold surfaces. Two classes of NHCs, based on imidazole and benzimidazole scaffolds, were tested. The resulting AuNP surfaces were analyzed using X-ray photoelectron spectroscopy (XPS), laser desorption ionization mass spectrometry (LDI-MS), and surface-enhanced Raman spectroscopy (SERS). Reaction of either a Au( i ) or Ag( i ) isopropyl benzimidazole NHC complex with citrate-capped AuNPs yields, in both cases, a chemisorbed NHC that is bound through a Au adatom. Theoretical calculations additionally illustrate that binding through the Au adatom is favored by more than 10 kcal mol −1 , in good agreement with experiments. Surprisingly, reaction of Au( i ), Ag( i ), and Cu( i ) diisopropylphenyl imidazole NHCs do not follow the same pattern. The Cu complex undergoes transmetalation with very little deposition of Cu; whereas, unexpectedly, the Ag complex foregoes transmetalation and instead adducts to the AuNP with retention of the Ag–C bond. Theoretical calculations illustrate that the imidazole ligand affords significant dispersion interactions with the gold surface, which may stabilize binding through the Ag adatom motif, despite its less favorable bonding energies. Taken together these results suggest a unique ability to tune the reactivity by changing the carbene structure and raise critical questions about how established transmetalation reactions in organometallic chemistry can be applied to form NHC functionalized surfaces. 

In this work, we extend a previously developed Raman bond model to periodic slab systems for interpreting chemical enhancements of surface-enhanced Raman scattering (SERS). The Raman bond model interprets chemical enhancements as interatomic charge flow modulations termed Raman bonds. Here, we show that the Raman bond model offers a unified interpretation of chemical enhancements for localized and periodic systems. As a demonstration of the Raman bond model, we study model systems consisting of CO and pyridine molecules on Ag clusters and slabs. We find that for both localized and periodic systems, the dominant Raman bonds are distributed near the molecule–metal interface and, therefore, the chemical enhancements are determined by a common Raman bond pattern. The effects of surface coverage, thickness, and roughness on the chemical enhancements have been studied, which shows that decreasing surface coverage or creating surface roughness increases chemical enhancements. In both of these cases, the inter-fragment charge flow connectivity is improved due to more dynamic polarization at the interface. The chemical enhancement is shown to scale with the inter-fragment charge flow to the fourth power. Since the inter-fragment charge flow is determined by the charge transfer excitation energy, the Raman bond model is connected to the transition-based analysis of chemical enhancements. We also show that the SERS spectra of localized and periodic systems normalized by inter-fragment charge flows can be unified. In summary, the Raman bond model offers a unique framework for understanding SERS spectra in terms of Raman bond distributions and offers a connection between localized and periodic model systems of SERS studies.