Barrierless photoisomerisation of the 'simplest cyanine': Joining computational and femtosecond optical spectroscopies to trace the full reaction path

摘要

The photoisomerisation of l,l'-diethyl-2,2'-pyridocyanine, regarded by Brooker as the simplest cyanine, is examined in methanol by time-resolved experiments and PCM/TD-CAM-B3LYP calculations. Femtosecond transient absorption, fluorescence upconversion, and stimulated Raman scattering, all with broadband coverage, provide a panoramic view of the photoreaction. On the computational side, evolving distributions on an S1 minimum-energy path are obtained by solving the Smoluchowski equation for drift and diffusion of torsional motion. Absorption and fluorescence bandshapes are calculated and compared to the observations; near-quantitative agreement implies that the entire S1 path has been observed. Most importantly the global S1 minimum, i.e. the perpendicular "phantom state" P*, can be identified and characterized in this way. Internal conversion of P~(*) (3.7 ps), assisted by solvent equilibration, leads to the hot ground state. Within 5 ps, vibrational bands of cts and trans isomers are recognized with the help of calculated Raman spectra. The differences between observed and simulated spectra are discussed.