The diffuse electron in a dipole-bound state is spatially well separated from the valence electrons and is known to have negligible effects on the dipole-bound state's molecular structure. Here, we show that a dipole-bound state is observed in deprotonated 4-(2-phenylethynyl)-phenoxide anions, 348 cm below the anion's detachment threshold. The photodetachment of the dipole-bound electron is observed to accompany a simultaneous shakeup process in valence orbitals in this aromatic molecular anion. This shakeup process is due to configuration mixing as a result of valence orbital polarization by the intramolecular electric field of the dipole-bound electron. This observation suggests that dipole-bound anions can serve as a new platform to probe how oriented electric fields influence the valence electronic structure of polyatomic molecules.
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