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Population Branching in the Conical Intersection of the Retinal Chromophore Revealed by Multipulse Ultrafast Optical Spectroscopy

The branching ratio of the excited-state population at the conical intersection between the S 1 and S 0 energy surfaces (φ CI) of a protonated Schiff base of all-trans retinal in protic and aprotic solvents was studied by multipulse ultrafast transient absorption spectroscopy. In particular, pump-dump-probe experiments allowed to isolate the S 1 reactive state and to measure the photoisomerization time constant with unprecedented precision. Starting from these results, we demonstrate that the polarity of the solvent is the key factor influencing the φ CI and the photoisomerization yield.

retinal ; conical intersection ; ultrafast spectroscopy ; photoisomerization

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