Non‐Ergodic Behavior of Excited Radical Cations in the Gas Phase

Abstract

That one of the central assumptions of the quasi-equilibrium theory (QET) of mass spectrometry can be violated is shown experimentally for the first time by the example of (1). The central assumption in question is the statistical distribution of the internal energy over the vibrational states of the reacting systems. The radicals 13CH3 and 12CH3 are eliminated in unequal proportions from (1a) and (1b)—in consequence the radical cations behave non-ergodically.