Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non‐Ergodic Behavior of Medium‐Sized Ion Pairs?

Abstract

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. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.