基于超快多维振动光谱技术解析分子体系的三维空间构型

超快多维振动光谱技术目前已经被广泛应用到各种凝聚态分子体系中分子的结构以及快速变化动力学过程的测量之中,并有望成为新一代解析分子体系微观结构及超快行为的常规手段。本文从两个主线出发,介绍如何利用超快多维振动光谱技术解析分子体系的三维空间构型。一方面通过测量分子内各个振动模式跃迁偶极矩间的夹角来获得分子体系内不同基团的相对空间取向,并最终确定分子的空间构型。另一方面,通过详细解析分子间振动能量转移的机理,进而将实验中测得的振动能量转移速率转化为分子之间的距离信息。

Determining 3D Molecular Conformations with Ultrafast Multiple-Dimensional Vibrational Spectroscopy

In recent years, ultrafast multiple-dimensional vibrational spectroscopy has been widely applied to studies of molecular structures and ultrafast dynamics in various condensed phases, and is expected to become a new generation of routine analytical tool for determining microstructures and ultrafast behaviors in molecular systems. In this review, we introduce in detail a method of determining three-dimensional (3D) molecular conformations with ultrafast multiple-dimensional vibrational spectroscopy. The introduction of our research follows two directions:(1) obtaining relative spatial orientations of different groups in a molecular system and finally determining molecular conformations by measuring cross angles of vibrational transition dipole moments; and (2) exploring the nature of vibrational energy transfers and determining molecular distances with experimentally measured vibrational energy transfer rates.