Vibrational state-selected photodissociation of ClO+

We report on the UV photodissociation of specific vibrational states (v = 2–45) of ClO+ using velocity map <br/>ion imaging. The high vibrational states of ClO+ are prepared via a double resonant scheme through the <br/>ClO (A 2P) state and ion-pair states followed by photoionization with a third photon. The absorption of a <br/>fourth photon results in photodissociation of the ClO+ into two dominant asymptotic channels. The Cl+ <br/>and O+ fragment ion images reveal information on both the energetics of high-lying cation vibrational <br/>states and the low-lying dissociative electronic states that correlate to Cl+(3P) + O(3P) and Cl(2P) + O+(4S) <br/>asymptotic channels. We also report ab initio potentials for the bound ClO+ and ion-pair states as well as <br/>calculations of the ClO+ excited states relevant to the photodissociation process.