Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non-Ergodic Behavior of Medium-Sized Ion Pairs?
2012
Abstract
Binary ion pairs of two conformers of an oligocyclic bispyridinium ion with triflate counterions show significant deviations between the infrared-multiphoton dissociation (IRMPD) spectra of the mass-selected ions in the gas phase compared to the infrared (IR) spectra of the bulk compounds as well as the computed IR spectra. As a possible explanation, incomplete intramolecular vibrational energy redistribution (IVR) is suggested which leads to an "overheating" of the triflate, once the S=O stretching modes are excited.