A multireference perturbation study of the NN stretching frequency of trans-azobenzene in nπ* excitation and an implication for the photoisomerization mechanism.

A multireference second-order perturbation theory is applied to calculate equilibrium structures and vibrational frequencies of trans-azobenzene in the ground and nπ* excited states, as well as the reaction pathways for rotation and inversion mechanism in the nπ* excited state. It is found that the NN stretching frequency exhibits a slight increase at the minimum energy structure in the nπ* state, which is explained by the mixing of the NN stretching mode with the CN symmetric stretching mode. We also calculate the NN stretching frequency at several selected structures along the rotation and inversion pathways in the nπ* state, and show that the frequency decreases gradually along the rotation pathway while it increases by ca. 300 cm(-1) along the inversion pathway. The frequencies and energy variations along the respective pathways indicate that the rotation pathway is more consistent with the experimental observation of the NN stretching frequency in nπ* excitation.