TD-DFT study of BIPS spiropyran: Effects of functionals and high-polarity solvent on C O bond dissociation and recovery.

We performed a theoretical analysis of the BIPS photochemical cycle using an extensive set of forty hybrid functionals and taking into account a highly polar solvent (methanol). The functionals with a small fraction of the exact Hartree-Fock exchange (%HF) showed the predominant S  → S transition with the strengthening of the C O bond. At the same time, functionals with medium and high %HF (including those with long-range correction) gave a dominant S  → S transition with weakening or breaking of the C O bond, which corresponds to the experimental results. The influence of a highly polar solvent on the photochemical electrocyclic transformations of BIPS turned out to be significant. The number of functionals causing dissociation of the C O bond decreased from 10 to 7 compared to the gas phase. The magnitude of the oscillator strength has increased by approximately one and a half times. Structural distortions of the BIPS molecule during excitation (both with and without C O bond cleavage) significantly decreased in methanol compared to the gas phase. The two strong hydrogen bonds of methanol molecules with the oxygen and nitrogen atoms of spiropyran also have a significant effect on its excitation. They lead to a change in the predominant transition from S  → S to S  → S for five functionals. The number of functionals giving dissociation of the C O bond decreased from seven to four (M08HX, M052X, CAM-B3LYP, and M11). After the opening of the excited BIPS molecule, both of its strong H-bonds with methanol are preserved. Of this set of four functionals, only M052X and CAM-B3LYP exhibited the dominant HOMO-1 → LUMO configuration observed in high-level computations by other authors. Therefore, both of these functionals are recommended for modeling the photochemical cycle of this spiropyran. The photochemical cycle of BIPS was theoretically analyzed. The redistribution of the electron density in this cycle was quantitatively described using the differences in NPA of the atomic charges. The most important result of this analysis was the electrostatic mechanism of the approach of C and oxygen atoms at the fourth stage, which causes further reduction of the C O bond.