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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.
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Understanding chemical enhancements of surface-enhanced Raman scattering using a Raman bond model for extended systems
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.
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- Award ID(s):
- 2106151
- PAR ID:
- 10560325
- Publisher / Repository:
- AIP Publishing
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 18
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1063/5.0124553
