On the Photoabsorption by Permanganate Ions in Vacuo and the Role of a Single Water Molecule. New Experimental Benchmarks for Electronic Structure Theory |
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| Authors: | Jørgen Houmøller Sydney H Kaufman Dr Kristian Støchkel Prof Lokesh C Tribedi Prof Steen Brøndsted Nielsen Prof J Mathias Weber |
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| Institution: | 1. Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, 8000 Aarhus C (Denmark);2. JILA and Department of Chemistry & Biochemistry, University of Colorado, 440 UCB, Boulder, CO 80309‐0440 (USA);3. Department of Nuclear and Atomic Physics, Tata Institute of Fundamental Research Colaba, Mumbai 400005 (India) |
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| Abstract: | 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 Mn? O 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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| Keywords: | gas‐phase spectroscopy mass spectrometry permanganate quantum chemistry single water complex |
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