The mechanism of the photoisomerisation of azobenzene has been studied by means of multiconfigurational ab initio calculations. Our results show that it is necessary to account for the dynamic electron correlation in the location of the critical points (CASPT2 optimizations) to obtain a correct description of the topography of the potential energy surfaces of the low energy singlet excited states. By using this methodology, we have found that the state populated by the initial excitation is the S2 (ππ*) state, which decays very efficiently to the S1 (nπ*) state at a pedal-like non-rotated geometry. In the S1 state, relaxation leads to a rotated geometry where the system decays to the ground state, in which further relaxation can lead to either the trans or cis geometries. However, the S1 /S0 conical intersection seam also extends to planar geometries, so this reaction path is also accessible for rotation-constrained systems. Our results explain the experimental observations satisfactorily.
Keywords: ab initio calculations; azo compounds; photoisomerisation; reaction mechanisms.
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