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Periodic decay in the photoisomerisation of p-aminoazobenzene.

Semiempirical OM2/MRCI surface-hopping simulations have been performed to study the E→Z and Z→E isomerisations of p-aminoazobenzene upon photoexcitation to the S1 state (nπ*). The overall mechanism is similar to the one found previously for the unsubstituted parent system, although there is a moderate speedup of the decay to the ground state because of the steeper excited-state potential between the Franck-Condon region and the conical intersection seam. The decay dynamics to the ground state shows an oscillatory pattern that can be attributed to an out-of-plane rotation of the N2 moiety. The reaction is thus initially driven by N2 rotation, which triggers phenyl rotations around the C-N bonds. The Z isomer is produced most effectively when the phenyl rings rotate in phase.