Excited state dynamics of aniline homoclusters

We have investigated the relaxation, following excitation in the 290–235 nm region, of neutral aniline homoclusters (An)n formed in a supersonic expansion by femtosecond time resolved ionization. The applied method permits isolation of the dynamics of the dimer from that originated in bigger species of the generated distribution. Interestingly, and differently from the monomer and (An)n≥3 clusters, the dimer does not present a N–H dissociative 1πσ* channel. This fact can be explained in terms of the symmetric structure adopted, in which each molecule establishes two N–H⋯π interactions, destabilizing the H dissociation channel. The observations permit relating the photophysics to the interactions established by the aniline units and confirming previous observations and theoretical predictions on the structure of aniline aggregates.