Abstract Over the last decade, ultrafast two-dimensional infrared (2D IR) spectroscopy has been greatly advanced in a variety of aspects and is becoming a more exciting vibrational tool for understanding the structures and dynamics of condensed-phase equilibrium and non-equilibrium molecular systems, as well as surface-immobilised monolayers or adsorbates. A number of novel multi-pulse experimental schemes have been reported, some of them allow one to simultaneously examine anharmonic vibrational interactions and frequency–frequency correlations among vibrational chromophores having very different vibrational frequencies, particularly in a broadband fashion, providing potentially intrinsic spectroscopic probes for local, regional, and global molecular structures and dynamics; and some of them allow one to access more vibrational levels of a given set of anharmonic oscillators, enabling a better characterisation of their anharmonic potentials and factors influencing them. In this review, we first introduce these basic experimental schemes, mainly focusing on the time-domain methods. We then introduce technological and experimental advances on 2D IR signal detections that can provide much higher spectral resolution and higher sensitivities. Together, these advances can further increase the capacities of these nonlinear infrared methods. Computational considerations and developments on assessing more anharmonic potential parameters and simulating correlated broadband 2D IR spectra are then followed. Examples of the applications of these experimental and theoretical methods are also provided and discussed. We finally conclude this review by summarising these recent developments of the 2D IR methodologies and by discussing more advanced multi-pulse nonlinear IR experiments and their potential applications in near future.

中文翻译：

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用于分子结构和动力学的超快二维红外光谱，波长范围不断扩大，灵敏度不断提高：从实验和计算的角度来看

摘要 在过去十年中，超快二维红外 (2D IR) 光谱在各个方面都取得了巨大进步，并且正在成为一种更令人兴奋的振动工具，用于了解凝聚相平衡和非平衡分子系统的结构和动力学。 ，以及表面固定的单层或吸附物。已经报道了许多新颖的多脉冲实验方案，其中一些允许同时检查具有非常不同振动频率的振动生色团之间的非谐振动相互作用和频率-频率相关性，特别是在宽带方式中，为局部、区域和全球分子结构和动力学；其中一些允许人们访问一组给定的非谐振荡器的更多振动水平，从而能够更好地表征它们的非谐势和影响它们的因素。在这篇综述中，我们首先介绍了这些基本的实验方案，主要集中在时域方法上。然后，我们介绍了 2D IR 信号检测的技术和实验进展，可以提供更高的光谱分辨率和更高的灵敏度。总之，这些进步可以进一步提高这些非线性红外方法的能力。然后遵循有关评估更多非谐波势参数和模拟相关宽带 2D IR 光谱的计算考虑和发展。还提供并讨论了这些实验和理论方法的应用示例。