TD-DFT analysis of excitation of the closed-form spironaphthopyran in methanol solution: The contribution of vibronic transitions and intermolecular hydrogen bonds.

A set of forty hybrid functionals, combined with a 6-31++G(d,p) basis set and an IEFPCM solvent description, was applied to calculate the S0→S1 excitation of the spironaphthopyran (SNP) photochromic compound. None of the hybrid functionals resulted in Cspiro-O bond cleavage upon optimization of the S1 excited state of the SNP, in contrast to the spiropyran BIPS which we studied earlier. At the same time, the deformations of the SNP during excitation turned out to be very small (in contrast to those for BIPS) which made it possible to calculate its vibronic absorption spectrum. The best agreement between the calculated and experimental absorption bands was demonstrated by the SOGGA11X functional. The main result of this work is confirmation of the vibration participation in the breaking of the Cspiro-O bond in the S1 excited state of the SNP. This assumption based on experimental data was previously put forward by other authors. Strong H-bonds between the SNP and two methanol molecules enhance the photoinduced distortions of the latter and are slightly weakened upon excitation.