Theoretical Insights into the Ultrafast Deactivation Mechanism and Photostability of a Natural Sunscreen System: Mycosporine Glycine.

In this work, different levels of quantum computational models such as MP2, ADC(2), CASSCF/CASPT2, and DFT/TD-DFT have been employed to investigate the photophysics and photostability of a mycosporine system, mycosporine glycine (MyG). First of all, a molecular mechanics approach based on the Monte Carlo conformational search has been employed to investigate the possible geometry structures of MyG. Then, comprehensive studies on the electronic excited states and deactivation mechanism have been conducted on the most stable conformer. The first optically bright electronic transition responsible for the UV absorption of MyG has been assigned as the S 2 ( 1 ππ*) owing to the large oscillator strength (0.450). The first excited electronic state (S 1 ) has been assigned as an optically dark ( 1 nπ*) state. From the nonadiabatic dynamics simulation model, we propose that the initial population in the S 2 ( 1 ππ*) state transfers to the S 1 state in under 100 fs, through an S 2 /S 1 conical intersection (CI). The barrierless S 1 potential energy curves then drive the excited system to the S 1 /S 0 CI. This latter CI provides a significant route for ultrafast deactivation of the system to the ground state via internal conversion.