Jump to main content
Jump to site search

Issue 48, 2011
Previous Article Next Article

Vibrational analysis of excited and ground electronic states of all-transretinal protonated Schiff-bases

Author affiliations

Abstract

We report on vibrational coherence dynamics in excited and ground electronic states of all-transretinal protonated Schiff-bases (RPSB), investigated by time-resolved Degenerate Four-Wave-Mixing (DFWM). The results show that wave packet dynamics in the excited state of RPSB consist of only low-frequency (<800 cm−1) modes. Such low-frequency wave packet motion is observed over a broad range of detection wavelengths ranging from excited state absorption (∼500 nm) to stimulated emission (>600 nm). Our results indicate that low-frequency coherences in the excited state are not activated directly by laser excitation but rather by internal vibrational energy redistribution. This is supported by the observation that similar coherence dynamics are not observed in the electronic ground state. Challenging previous experimental results, we show that the formation of low-frequency coherence dynamics in RPSB does not require significant excess vibrational energy deposition in the excited state vibrational manifolds. Concerning ground state wave packet dynamics, we observe a set of high-frequency (>800 cm−1) modes, reflecting mainly single and double bond stretching motion in the retinal polyene-chain. Dephasing of these high-frequency coherences is mode-dependent and partially differs from analogous vibrational dephasing of the all-transretinal chromophore in a protein environment (bacteriorhodopsin).

Graphical abstract: Vibrational analysis of excited and ground electronic states of all-transretinal protonated Schiff-bases

Back to tab navigation

Publication details

The article was received on 09 Jul 2011, accepted on 10 Oct 2011 and first published on 28 Oct 2011


Article type: Paper
DOI: 10.1039/C1CP22245G
Citation: Phys. Chem. Chem. Phys., 2011,13, 21402-21410

  •   Request permissions

    Vibrational analysis of excited and ground electronic states of all-transretinal protonated Schiff-bases

    J. P. Kraack, T. Buckup and M. Motzkus, Phys. Chem. Chem. Phys., 2011, 13, 21402
    DOI: 10.1039/C1CP22245G

Search articles by author

Spotlight

Advertisements