We report that the photoinduced dynamics of the phytochrome chromophore is strongly dependent on the protonation/deprotonation states of the pyrrole ring. The on-the-fly surface hopping dynamics simulations were performed to study the photoisomerization of different protonation/deprotonation phytochrome chromophore models. The simulation results indicate that the deprotonations at the pyrrole rings significantly modify the photoinduced nonadiabatic dynamics, leading to distinctive population decay dynamics and different reaction channels. Such feature can be well explained by the formation of the different hydrogen bond network patterns. Therefore, the proper understanding of the photoisomerization mechanism of phytochrome chromophore must take the hydrogen bond network into account. This work provides the new insights into the photobiological functions of phytochrome chromophore and suggests the possible ideas to control of its photoconversion processes for further rational engineering in optical applications.
SI for Significant Impact of Deprotonated Status on the Photoisomerization Dynamics of Bacteriophytochrome Chromophore