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We report a study of the diazabicyclo[2.2.2]octane (DABCO) molecule photoionized using VUV synchrotron radiation in combination with an ion–electron coincidence spectrometer. We determine accurately the adiabatic ionization energy to ~eV. Two vibrational progressions of DABCO cation ground state are resolved at and , which we assign to modes of symmetry. Analysis of the photoelectron angular distribution shows that the anisotropy parameter depends on the vibrational excitation. This dependence of the parameter with the vibrational excitation is attributed to the scattering of the outgoing wavefunction mediated by high-lying Rydberg states.

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