This article provides an overview of some of the recent advances in the rapidly growing field of negative-ion photoelectron imaging spectroscopy. Setting the work that spans several projects in the authors’ laboratory in broader context, three types of measurements are described. First are the ‘static’ (one-photon) photoelectron imaging experiments that aim to characterize the electronic structure and photodetachment dynamics of negative ions, providing ‘signatures’ of the bound electron orbitals. The experimental results are presented alongside a conceptual symmetry-based description of the photodetachment processes, enabling a qualitative interpretation of the photoelectron images. Second, the effects of solvation on the electronic structure and photodetachment dynamics are examined using photoelectron imaging of cluster anions. Third, the time-resolved experiments that target imaging of bond dissociation, as viewed from the electronic perspective along the time-resolved reaction coordinate, are described in the context of dual centre interference in molecular-anion photodetachment.
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