Experimental assignments of the 3p Rydberg states of acetone

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Abstract
A polarization‐selected two‐ and three‐photon resonant multiphoton ionization investigation of the 3p Rydberg region of the spectra of acetone and acetone‐d6 has been conducted to resolve the controversy concerning 3p Rydberg assignments. Here the 3p Rydberg transitions of acetone are unambiguously assigned. The assigned spectra are then used to assess excited state energy calculations of acetone and to evaluate empirical electron energy loss spectroscopy rules. The vibrational substructures of the Rydberg ←n transitions are used to deduce structural and dynamical information about the Rydberg states of acetone and suggest a possible misassignment of the ground state vibrational spectrum.