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Updated: Jul 19, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Dissociative photodetachment dynamics of the iodide-aniline cluster
M Shane Bowen1, Maurizio Becucci, Robert E Continetti
1Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093-0340, USA.
Abstract:
The photodetachment dynamics of the iodide-aniline cluster, I-(C6H5NH2), were investigated using photoelectron-photofragment coincidence spectroscopy at several photon energies between 3.60 and 4.82 eV in concert with density functional theory calculations. Direct photodetachment from the solvated I- chromophore and a wavelength-independent autodetachment process were observed. Autodetachment is attributed to a charge-transfer-to-solvent reaction in which incipient continuum electrons photodetached from I- are temporarily captured by the nascent neutral iodine-aniline cluster configured in the anion geometry. Subsequent dissociation of the neutral cluster removes the stabilization, leading to autodetachment of the excess electron. The dependence of the dissociative photodetachment (DPD) and autodetachment dynamics on the final spin-orbit electronic state of the iodine fragment is characterized. The dissociation dynamics of the neutral fragments correlated with autodetached electrons were found to be identical to the DPD dynamics of the I atom product spin-orbit state closest to threshold at a given photon energy, lending support to the proposed sequential mechanism.
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