Simultaneously Probing Two Ultrafast Condensed‐Phase Molecular Symmetry Breaking Events by Two‐Dimensional Infrared Spectroscopy

In condensed phases, a highly symmetric gas‐phase molecule lowers its symmetry under perturbation of the solvent, which is vital to a variety of structural chemistry related processes. However, the dynamical aspects of solvent‐mediated symmetry‐breaking events remain largely unknown. Herein, direct evidence for two types of solvent‐mediated symmetry‐breaking events that coexist on the picosecond timescale in a highly symmetric anion, namely, hexacyanocobaltate, is presented: 1) an equilibrium symmetry‐breaking event in which a solvent‐bound species having lowered symmetry undergoes a population exchange reaction with the symmetry‐retaining species; 2) a dynamic symmetry‐breaking event that is composed of many dynamic population‐exchange reactions under fluctuating solvent interactions. Ultrafast two‐dimensional infrared spectroscopy is used to simultaneously observe and dynamically characterize these two events. This work opens a new window into molecular symmetry and structural dynamics under equilibrium and non‐equilibrium conditions.