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Toward a consistent view of chemical mechanism of SERS: theoretical formalisms versus experimental observations
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DOI：10.1080/05704928.2026.2671847.png)
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Abstract
En 中文
Although the chemical enhancement mechanism (CEM) in surface-enhanced Raman scattering (SERS) has been discussed for several decades, the magnitude, spectral selectivity, and physical origin of the resulting chemical contributions remain unresolved. In this review, we revisit CEM with the aim of clarifying how commonly used theoretical descriptions relate to experimentally observed Raman features. We consider three regimes that are typically invoked in the context of CEM: non-resonant scattering (Placzek approximation), intramolecular resonance (Albrecht A-term), and interfacial charge-transfer (CT) processes (HT coupling). Rather than treating these regimes as strictly separate, we emphasize their frequent spectral overlap and focus on experimental signatures, such as excitation profiles, depolarization ratios, and mode selectivity, and how these reflect the underlying electronic and vibronic structure. We also address inconsistencies between theory and experiment, including enhancement factors and the broadening of CT-related features, and discuss the importance of interfacial dynamics. Finally, we highlight recent developments involving non-equilibrium effects and hybrid regimes in which electromagnetic fields are strongly coupled to interfacial electronic processes, making the separation between enhancement contributions increasingly difficult. This review aims to provide a more consistent perspective on CEM in SERS and to outline the key open challenges.
Keywords:
SERS
chemical mechanism
theoretical formalism
charge-transfer
consistent view
Journal
A
IF:
5.4
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779
Citations:
3.7K
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