Vibrational state-selected photodissociation of ClO+

► We have photodissociated specific vibrational states (v = 2-45) of ClO+ via ion-pair states. ► Ion-pair states permit access to high lying ClO+ states not previously observed. ► Ion imaging was utilized to study the photodissociation dynamics of the ClO+. ► We present new ab initio potentials for ClO+ excited states and ClO ion-pair states.