We report electronic spectra of mass-selected MnO4− and MnO4−⋅H2O using electronic photodissociation spectroscopy. Bare MnO4− fragments by formation of MnO3− and MnO2−, while the hydrated complex predominantly decays by loss of the water molecule. The band in the visible spectral region shows a well-resolved vibrational progression consistent with the excitation of a MnO stretching mode. The presence of a single water molecule does not significantly perturb the spectrum of MnO4−. Comparison with the UV/Vis absorption spectrum of permanganate in aqueous solution shows that complete hydration causes a small blueshift, while theoretical models including a dielectric medium have predicted a redshift. The experimental data can be used as benchmarks for electronic structure theory methods, which usually predict electronic spectra in the absence of a chemical environment.
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