Detailed mechanism of trans-cis photoisomerization of azobenzene studied by semiclassical dynamics simulation

摘要

A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene. The simulation follows both n pi* and pi pi* excitations and each excitation is induced by a 50 fs (FWHM) laser pulse. The simulation results show that, for both excitations, the reaction path is predominated by the rotation coordinate of the NN bond. The simulation finds that the CNN inversion angles expand as soon as the rotation starts. The expansion of the CNN bond angles permits the molecule to rotate efficiently. It is therefore suggested that the photoisomerization of trans-azobenzene follows an inversion-assisted rotation path. These simulation results are significant for understanding the mechanism of this important process.