PMID- 22033578 OWN - NLM STAT- MEDLINE DCOM- 20120321 LR - 20131121 IS - 1463-9084 (Electronic) IS - 1463-9076 (Linking) VI - 13 IP - 48 DP - 2011 Dec 28 TI - Vibrational analysis of excited and ground electronic states of all-trans retinal protonated Schiff-bases. PG - 21402-10 LID - 10.1039/c1cp22245g [doi] AB - We report on vibrational coherence dynamics in excited and ground electronic states of all-trans retinal 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 ( approximately 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-trans retinal chromophore in a protein environment (bacteriorhodopsin). FAU - Kraack, Jan Philip AU - Kraack JP AD - Physikalisch-Chemisches Institut, Ruprecht-Karls Universitat Heidelberg, D-69210 Heidelberg, Germany. FAU - Buckup, Tiago AU - Buckup T FAU - Motzkus, Marcus AU - Motzkus M LA - eng PT - Journal Article DEP - 20111028 PL - England TA - Phys Chem Chem Phys JT - Physical chemistry chemical physics : PCCP JID - 100888160 RN - 0 (Protons) RN - 0 (Schiff Bases) RN - 53026-44-1 (Bacteriorhodopsins) RN - RR725D715M (Retinaldehyde) SB - IM MH - Bacteriorhodopsins/chemistry MH - Isomerism MH - Protons MH - Quantum Theory MH - Retinaldehyde/*chemistry MH - Schiff Bases/*chemistry MH - Vibration EDAT- 2011/10/29 06:00 MHDA- 2012/03/22 06:00 CRDT- 2011/10/29 06:00 PHST- 2011/10/29 06:00 [entrez] PHST- 2011/10/29 06:00 [pubmed] PHST- 2012/03/22 06:00 [medline] AID - 10.1039/c1cp22245g [doi] PST - ppublish SO - Phys Chem Chem Phys. 2011 Dec 28;13(48):21402-10. doi: 10.1039/c1cp22245g. Epub 2011 Oct 28.