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Abstract
Gas-phase charge-transfer electronic spectroscopy was utilized to probe Ag+(benzene) and Ag+(toluene) complexes. These ions were generated via laser vaporization in a pulsed supersonic expansion then mass-selected and photodissociated using a tunable UV-Vis OPO laser. Electronic excitation spectra were measured via a metal to ligand charge-transfer process in which the organic cation was exclusively generated. Measuring the wavelength dependence of photodissociation resulted in broad, featureless absorptions that were identified as the charge-transfer state and a silver excited electronic state. The threshold for the dissociation energy of both complexes was determined from an excitation to the repulsive wall of the charge-transfer excited states. Computational work was completed in tandem using TD-DFT and predicted both excited state absorptions with relative success. These results in combination with previous work illuminated new energetics for the cation-π interactions in these complexes.