Heterodimers of fluorobenzene (FB) with 1,4‐dioxane and methanol were synthesized in a seeded supersonic beam and studied by resonant two‐photon ionization combined with TOF mass spectrometry. The electronic spectra near the origin of the S1(π π*)← S0 transition of FB revealed solvent induced shifts and spectral features due to the excitation of van der Waals modes. In addition, strong dynamic behaviour of the photo‐ionized dimers could be observed.
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