Ultraviolet and visible light photodissociation of H3+ in an ion storage ring

J Phys Chem A. 2010 Apr 15;114(14):4864-9. doi: 10.1021/jp9104163.

Abstract

Ultraviolet and visible photodissociation of a vibrationally excited H(3)(+) ion beam, as produced by standard ion sources, was successfully implemented in an ion storage ring with the aim of investigating the decay of the excited molecular levels. A collinear beams configuration was used to measure the photodissociation of H(3)(+) into H(2)(+) + H fragments by transitions into the first excited singlet state with 266 and 532 nm laser beams. A clear signal could be observed up to 5 ms of storage, indicating that enough highly excited rovibrational states survive on the millisecond time scale of the experiment. The decay into H(2)(+) + H shows an effective time constant between about 1 and 1.5 ms. The initial photodissociating states are estimated to lie roughly 1 eV below the dissociation limit of 4.4 eV. The expected low population of these levels gives rise to an effective cross section of several 10(-20) cm(2) for ultraviolet and some 10(-21) cm(2) for visible light. For using multistep resonant dissociation schemes to monitor rotational populations of cold H(3)(+) in low-density environments, these measurements open promising perspectives.