Communication breakdown: Ergodicity is the ability to predict the behavior of an ensemble from the behavior of its components. Infrared spectroscopy of mass-selected ion pairs in the gas phase suggests that intramolecular vibrational energy redistribution (IVR) is hindered in some of these noncovalently bound species, particularly when triflate anion is involved. The hindered IVR leads to a non-ergodic behavior on a timescale sufficient for the formation of new chemical bonds.
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