This deviation may originate from the neglecting of second-order SVC contribution, the inaccurate potential energy surfaces provided by TDDFT with TDA, and the improper description of complex experimental environment in our calculations. In our theoretical calculations, we assume a single molecule in the dilute solution and the solvent effect is accounted for by the PCM. The solute-solute and explicit solute-solvent intermolecular interactions, and the effect of environmental fluctuation are not taken into account, which would slow these transition processes down.