Toward Modeling the Complexity of the Chemical Mechanism in SERS

Surface-enhanced Raman scattering (SERS) provides detailed information about the binding of molecules at interfaces and their interactions with the local environment due to the large enhancement of Raman scattering. This enhancement arises from a combination of the electromagnetic mechanism (EM) and chemical mechanism (CM). While it is commonly accepted that EM gives rise to most of the enhancement, large spectral changes originate from CM. To elucidate the rich information contained in SERS spectra about molecules at interfaces, a comprehensive understanding of the enhancement mechanisms is necessary. In this Perspective, we discuss the current understanding of the enhancement mechanisms and highlight their interplay in complex local environments. We will also discuss emerging areas where the development of computational and theoretical models is needed with specific attention given to how the CM contributes to the spectral changes. Future efforts in modeling should focus on overcoming the challenges presented in this review in order to capture the complexity of CM in SERS.