Coherent vibrational dynamics of retinal in excited electronic states are of primary importance in the understanding of photobiology. Using pump-DFWM, we demonstrate for the first time the existence of coherent double-bond high-frequency modulations (>1300 cm(-1)) in the excited electronic state of different retinal derivatives. All-trans retinal as well as retinal Schiff bases exhibit a partial frequency downshift of the C═C double-bond mode from ∼1580 cm(-1) in the ground state to 1510 cm(-1) in the excited state. In addition, a new vibrational band at ∼1700 cm(-1) assigned to the C═N stretching mode in retinal Schiff bases in the excited state is detected. The newly reported bands are observed only in specific spectral regions of excited-state absorption. Implications regarding the observation of vibrational coherences in naturally occurring retinal protonated Schiff bases in rhodopsins are discussed.
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Kraack et al. (2013) studied this question.