Charge Transfer Driven Structural Relaxation in a Push-Pull Azobenzene Dye-Semiconductor Complex.

Photoexcited structural dynamics in azo-compounds may differ fundamentally whether the push-pull photochromic azo-compound is isolated or forms a heterogeneous charge transfer complex, due to a sudden oxidation of the chromophore. Herein, we use a quantum-classical self-consistent approach that incorporates nonadiabatic excited-state electronic quantum dynamics into molecular mechanics to study the photoexcited dynamics of the push-pull azo-compound para-Methyl Red in the gas phase and sensitizing the (101) anatase surface of TiO2. We find that the photoinduced S-2/S-0 trans-to-cis isomerization of para-Methyl Red in the gas phase occurs through a pedal-like torsion around the phi(CNNC) dihedral angle, without evidence to support the inversion mechanism, likewise in the parent azobenzene molecule. However, the photoexcited structural relaxation of the charge transfer complex para-Methyl Red/TiO2 contrasts essentially with the isolated azo-compounds. Immediately after photoexcitation, the excited electron flows into the TiO2 conduction band, with an injection time constant of similar or equal to 5 fs, and no indication of isomerization is observed during the 1.5 ps simulations. Instead, a strong vibronic relaxation occurs that excites the NN stretching mode of the azo-group, which is ultimately ascribed to the NA relaxation, and delocalization, of the hole wavepacket.