Too much heat in non-covalent complexes leads to non-ergodic behavior in ion pairs of nitrogen-containing cations with triflate counterions. In their Communication on page 10050 ff., D. Schröder et al. show by means of infrared spectroscopy of mass-selected ions that the effect is caused by incomplete intramolecular vibrational energy distribution, leading to a local “overheating” of the triflate counterions. PS: Find the hidden dedication in the picture! The puzzle will be solved on the homepage of ChemViews Magazine (http://www.chemviews.org).