Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.

中文翻译：

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等离子体激元驱动反应的纳米结构表征

电磁辐射对贵金属纳米结构的照明会在其表面上诱导导电电子的相干振荡。电子的这些相干振荡，也称为局部表面等离振子共振（LSPR），是来自金属表面附近的分析物拉曼散射电磁增强的根本物理原因。这种物理现象被广泛称为表面增强拉曼散射（SERS）。LSPR可以通过直接的带间，声子辅助的带内和几何结构的辅助跃迁而衰减，从而形成热载流子，这些高能物种负责多种化学转化。这篇评论批判性地讨论了在纳米尺度上机械阐明热载流子驱动的化学反应和催化过程的最新进展。该评论简要介绍了尖端增强拉曼光谱（TERS），这是一种具有单分子敏感性和埃空间分辨率的现代分析技术，显示了该技术在等离激元驱动反应的时空表征中的优势。该评论还讨论了实验和理论上的发现，这些发现报告了新型的等离激元驱动的反应性，可用于催化氧化还原，偶联，消除和剪切反应。最后，该综述讨论了最新报道的发现对等离子体催化和TERS成像的影响。展示了该技术在等离激元驱动反应的时空表征方面的优势。该评论还讨论了实验和理论上的发现，这些发现报告了新型的等离激元驱动的反应性，可用于催化氧化还原，偶联，消除和剪切反应。最后，该综述讨论了最新报道的发现对等离子体催化和TERS成像的影响。展示了该技术在等离激元驱动反应的时空表征方面的优势。该评论还讨论了实验和理论上的发现，这些发现报告了新型的等离激元驱动的反应性，可用于催化氧化还原，偶联，消除和剪切反应。最后，该综述讨论了最新报道的发现对等离子体催化和TERS成像的影响。