Vibrational predissociation and vibrationally induced isomerization of 3-aminophenol-ammonia.

We investigate the vibrational predissociation dynamics of the hydrogen-bonded 3-aminophenol-ammonia cluster (3-AP-NH3) in the OH and NH stretching regions. Vibrational excitation provides enough energy to dissociate the cluster into its constituent 3-AP and NH3 monomers, and we detect the 3-AP fragments via (1 + 1) resonance-enhanced multiphoton ionization (REMPI). The distribution of vibrational states of the 3-AP fragment suggests the presence of two distinct dissociation pathways. The first dissociation channel produces a broad, unstructured feature in the REMPI-action spectrum after excitation of any of the OH or NH stretching vibrations, pointing to a nearly statistical dissociation pathway with extensive coupling among the vibrations in the cluster during the vibrational predissociation. The second dissociation channel produces distinct, resolved features on top of the broad feature but only following excitation of the OH or symmetric NH3 stretch in the cluster. This striking mode-specificity is consistent with strong coupling of these two modes to the dissociation coordinate (the O-H⋯N bond). The presence of clearly resolved transitions to the electronic origin and to the 10a(2) + 10b(2) state of the cis-3-AP isomer shows that vibrational excitation is driving the isomerization of the trans-3-AP-NH3 isomer to the cis-3-AP-NH3 isomer in the course of the dissociation.