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 S₂/S₀ trans-to- cis isomerization of para-Methyl Red in the gas phase occurs through a pedal-like torsion around the ϕ_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 ≃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.