Unveiling the nonadiabatic photoisomerization mechanism of hemicyanines for UV photoprotection.

In this work, the nonadiabatic energy relaxation mechanism of hemicyanines for UV photoprotection were investigated by using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) method for the first time. The absorption spectra and potential energy surfaces (PESs) of four hemicyanines with different positions of substituents were presented. The maximum absorption peaks of the four hemicyanines are located in the UVA region. In addition, all these hemicyanine molecules also have light absorption in both the UVB and UVC regions. At the same time, we found that the trans-cis photoisomerization PESs of all these hemicyanines have a significant conical intersection (CI) point between the first excited state and the ground state. Herein, it was first demonstrated that the UV energy absorbed by the hemicyanines could be dissipated nonadiabatically through the CI point by using the trans-cis photoisomerization dynamics mechanism. This work proves that hemicyanines have the possibility to be applied for UV photoabsorbers, and provides important basis for designing new type of hemicyanines for UV photoprotection.