Abstract
The 2B 3u(π, π)←D 0( 2B 2g) transition of p-difluorobenzene ( p-DFB) cations prepared by two-color resonance-enhanced multiphoton ionization (REMPI) has been observed by mass-selected ion dip spectroscopy utilizing dissociation. All the spectra due to the transitions from different vibrational levels in D 0 showed vibrationally resolved structures. It was found from their vibrational analysis that there exists a strong vibronic coupling between the 2B 3u(π, π) state and the nearby (σ, π) state, and the former is the lowest excited state. The nonemissive property of p-DFB cation forms an exception to the generally accepted criterion that all fluorobenzene cations having the lowest excited (π, π) state are emissive.
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