In surface-enhanced Raman scattering (SERS), two complementary SERS enhancement mechanisms are known: electromagnetic enhancement (EME) and chemical enhancement (CE). Herein, we demonstrated, by exciting SERS with a well-suited laser wavelength near the localized surface plasmon resonance (LSPR) of gold nanorods (AuNRs), that the CE contribution to the SERS signal can be selectively tuned and quantified through its correlation with chemical interface damping (CID), one of the LSPR decay processes in AuNRs. We further elucidated probe electrophilicity of a series of para-substituted aromatic thiophenols through a strong gold–sulfur interaction that plays an important role in hot-electron charge transfer from AuNRs to adsorbates, effectively increasing the CE. Therefore, our findings reveal that strong CID must significantly increase the CE for SERS to allow tuning of the CE under resonant conditions.

中文翻译：

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化学界面阻尼在调谐化学增强在等离激元金纳米棒的共振表面增强拉曼散射中的作用

在表面增强拉曼散射（SERS）中，已知两种互补的SERS增强机制：电磁增强（EME）和化学增强（CE）。在此，我们证明了，通过在金纳米棒（AuNRs）的局部表面等离振子共振（LSPR）附近以合适的激光波长激发SERS，可以通过与化学物质的相关性来选择性地调谐和量化CE对SERS信号的贡献。界面阻尼（CID），即AuNRs中的LSPR衰减过程之一。我们进一步阐明了一系列对位的探针亲电性取代的芳族硫酚具有很强的金-硫相互作用，在从AuNRs到吸附物的热电子电荷转移中起着重要作用，有效地提高了CE。因此，我们的发现表明，强大的CID必须显着提高SERS的CE，以便在谐振条件下调整CE。