High-level Ab Initio Absorption Spectra Simulations of Neutral, Anionic and Neutral+ Chromophore of Green Fluorescence Protein Chromophore Models in Gas Phase and Solution

Semiclassical ab initio simulations of the absorption spectra of neutral and anionic p-hydroxybenzylidene-2,3-dimethylimidazolinone (p-HBDI), a model chromophore of green fluorescent protein (GFP) and of a positively charged neutral (N+)-HBDI chromophore model, were performed in gas phase with the resolution-of-identity algebraic diagrammatic construction through second-order (RI-ADC(2)) method. The calculated absorption spectra in gas phase are composed of one band centered at 3.51 eV (HBDI), 2.50 eV (HBDI⁻) and 3.02 eV ((N+)-HBDI) owing to the absorption of the first ¹ππ* transition. Band maxima are redshifted by ~0.1 eV with respect to the corresponding vertical energies. The COSMO-RI-ADC(2) calculations of the first vertical excitation energy of HBDI, HBDI⁻ and (N+)-HBDI forms in polar solution including microsolvation simulate the observed solvent redshift for neutral HBDI and the solvent blueshift of the HBDI⁻ and (N+)-HBDI forms. The state-specific solvation approach applied to TDDFT calculations reproduced the experimental solvent shifts for the three HBDI forms, demonstrating a more accurate theoretical description as compared to the linear-response TDDFT approach.