PMID- 30507189 OWN - NLM STAT- MEDLINE DCOM- 20191015 LR - 20191015 IS - 1520-5207 (Electronic) IS - 1520-5207 (Linking) VI - 122 IP - 51 DP - 2018 Dec 27 TI - Excited State Vibrational Spectra of All- trans Retinal Derivatives in Solution Revealed By Pump-DFWM Experiments. PG - 12271-12281 LID - 10.1021/acs.jpcb.8b08495 [doi] AB - The ultrafast structural changes during the photoinduced isomerization of the retinal-protonated Schiff base (RPSB) is still a poorly understood aspect in the retinal's photochemistry. In this work, we apply pump-degenerate four-wave mixing (pump-DFWM) to all- trans retinal (ATR) and retinal Schiff bases (RSB) to resolve coherent high- and low-frequency vibrational signatures from excited electronic states. We show that the vibrational spectra of excited singlet states in these samples exhibit pronounced differences compared to the relaxed ground state. Pump-DFWM results indicate three major features for ATR and RSB. (i) Excited state vibrational spectra of ATR and RSB consist predominately of low-frequency modes in the energetic range 100-500 cm(-1). (ii) Excited state vibrational spectra show distinct differences for excitation in specific regions of electronic transitions of excited state absorption and emission. (iii) Low-frequency modes in ATR and RSB are inducible during the entire lifetime of the excited electronic states. This latter effect points to a transient molecular structure that, following initial relaxation between different excited electronic states, does not change anymore over the lifetime of the finally populated excited electronic state. FAU - Kraack, Jan Philip AU - Kraack JP AUID- ORCID: 0000-0001-7078-0565 AD - Physikalisch-Chemisches Institut , Ruprecht-Karls Universitat Heidelberg , D-69210 Heidelberg , Germany. FAU - Motzkus, Marcus AU - Motzkus M AD - Physikalisch-Chemisches Institut , Ruprecht-Karls Universitat Heidelberg , D-69210 Heidelberg , Germany. FAU - Buckup, Tiago AU - Buckup T AUID- ORCID: 0000-0002-1194-0837 AD - Physikalisch-Chemisches Institut , Ruprecht-Karls Universitat Heidelberg , D-69210 Heidelberg , Germany. LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20181214 PL - United States TA - J Phys Chem B JT - The journal of physical chemistry. B JID - 101157530 RN - 0 (Schiff Bases) RN - RR725D715M (Retinaldehyde) SB - IM MH - Light MH - Retinaldehyde/*chemistry/radiation effects MH - Schiff Bases/chemistry/radiation effects MH - Spectrum Analysis/methods MH - Stereoisomerism MH - Vibration EDAT- 2018/12/07 06:00 MHDA- 2019/10/16 06:00 CRDT- 2018/12/04 06:00 PHST- 2018/12/07 06:00 [pubmed] PHST- 2019/10/16 06:00 [medline] PHST- 2018/12/04 06:00 [entrez] AID - 10.1021/acs.jpcb.8b08495 [doi] PST - ppublish SO - J Phys Chem B. 2018 Dec 27;122(51):12271-12281. doi: 10.1021/acs.jpcb.8b08495. Epub 2018 Dec 14.