Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 38, Pages 13350-13364Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp41522d
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Funding
- Deutsche Forschungsgemeinschaft [ER154/10-1]
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The photoisomerisation of 1,1'-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 S-1 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 S-1 path has been observed. Most importantly the global S-1 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 cis and trans isomers are recognized with the help of calculated Raman spectra. The differences between observed and simulated spectra are discussed.
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