Raman spectroscopy is a versatile tool for acquiring molecular structure information. The incorporation of plasmonic fields has significantly enhanced the sensitivity and resolution of surface-enhanced Raman scattering (SERS) and tip-enhanced Raman spectroscopy (TERS). The strong spatial confinement effect of plasmonic fields has challenged the conventional Raman theory, in which a plane wave approximation for the light has been adopted. In this review, we comprehensively survey the progress of a generalized theory for SERS and TERS in the framework of effective field Hamiltonian (EFH). With this approach, all characteristics of localized plasmonic fields can be well taken into account. By employing EFH, quantitative simulations at the first-principles level for state-of-the-art experimental observations have been achieved, revealing the underlying intrinsic physics in the measurements. The predictive power of EFH is demonstrated by several new phenomena generated from the intrinsic spatial, momentum, time, and energy structures of the localized plasmonic field. The corresponding experimental verifications are also carried out briefly. A comprehensive computational package for modeling of SERS and TERS at the first-principles level is introduced. Finally, we provide an outlook on the future developments of theory and experiments for SERS and TERS.

中文翻译：

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尖端和表面增强拉曼散射的理论和计算方法

拉曼光谱是获取分子结构信息的多功能工具。等离子体场的结合显着提高了表面增强拉曼散射（SERS）和尖端增强拉曼光谱（TERS）的灵敏度和分辨率。等离子体场强大的空间限制效应对传统的拉曼理论提出了挑战，传统的拉曼理论采用了光的平面波近似。在这篇综述中，我们全面综述了有效场哈密顿量（EFH）框架内的 SERS 和 TERS 广义理论的进展。通过这种方法，可以很好地考虑局域等离子体场的所有特征。通过采用 EFH，已经实现了最先进实验观测的第一原理水平的定量模拟，揭示了测量中潜在的内在物理现象。局域等离子体场的固有空间、动量、时间和能量结构产生的几种新现象证明了 EFH 的预测能力。并简要进行了相应的实验验证。介绍了用于第一原理级别的 SERS 和 TERS 建模的综合计算包。最后，我们对SERS和TERS的理论和实验的未来发展进行了展望。