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State-specific dynamics of the dipole-bound state (DBS) of the cryogenically cooled deprotonated 4,4'-biphenol anion have been investigated by picosecond time-resolved pump-probe spectroscopy. For DBS vibrational states below the electron-detachment threshold, the relaxation rate is slow to give a lifetime (τ) longer than ∼5 ns, and it is attributed to the nonvalence-to-valence orbital transformation. For the DBS resonances above the detachment threshold, however, the lifetime decreases with the activation of autodetachment, whereas the otherwise zeroth DBS modes seem to be randomized by intramolecular vibrational energy redistribution (IVR), as manifested in the biexponential transients. As the DBS internal energy increases further, the lifetime shows a monotonic decrease to give τ ∼ 50 ps at
Kim et al. (Wed,) studied this question.