Vibrational state-selected photodissociation of ClO+

Abstract

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