A velocity map imaging mass spectrometer for photofragments of fast ion beams.

We present the details of a fast ion velocity map imaging mass spectrometer that is capable of imaging the photofragments of trap-cooled (≥7 K) ions produced in a versatile ion source. The new instrument has been used to study the predissociation of N2O+ produced by electric discharge and the direct dissociation of Al2+ formed by laser ablation. The instrument's resolution is currently limited by the diameter of the collimating iris to a value of Δv/v = 7.6%. Photofragment images of N2O+ show that when the predissociative state is changed from 2Σ+(200) to 2Σ+(300) the dominant product channel shifts from a spin-forbidden ground state, N (4S) + NO+(v = 5), to a spin-allowed pathway, N*(2D) + NO+. The first photofragment images of Al2+ confirm the existence of a directly dissociative parallel transition (2Σ+u ← 2Σ+g) that yields products with a large amount of kinetic energy. D0 of ground state Al2+ (2Σ+g) measured from these images is 138 ± 5 kJ/mol, which is consistent with the published literature.