Unimolecular (metastable) and collision-induced dissociation of 1,3, 5-trinitrobenzene molecular ion was studied using linked scans and mass-analyzed ion kinetic energy spectrometry on a hybrid instrument of EBEqQ geometry. An unusual ortho effect leading to the loss of OH radical from the parent molecular ion is observed as a unimolecular dissociation process only in the first-field free region between the ion source and the electric sector, although corresponding dissociation in the ion source is of negligible abundance (<0.1%). This unimolecular process is taken over by other dissociation pathways when the parent ion is collisionally activated, suggesting that this dissociation process occurs only in a very narrow energy window with a rate constant of the order of 2 x 10(5) s(-1). Copyright 2000 John Wiley & Sons, Ltd.