Vibronic coupling in the excited-states of carotenoids

Miki, T., Buckup, T., Krause, M. S., Southall, J. , Cogdell, R. J. and Motzkus, M. (2016) Vibronic coupling in the excited-states of carotenoids. Physical Chemistry Chemical Physics, 18(16), pp. 11443-11453. (doi:10.1039/C5CP07542D) (PMID:27055720)

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Abstract

The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S2 to the optically dark state S1. Extending this picture, some additional dark states (3A−g and 1B−u) and their interaction with the S2 state have also been suggested to play a major role in the ultrafast deactivation of carotenoids and their properties. Here, we investigate the interaction between such dark and bright electronic excited states of open chain carotenoids, particularly its dependence on the number of conjugated double bonds (N). We focus on the ultrafast wave packet motion on the excited potential surface, which is modified by the interaction between bright and dark electronic states. Such a coupling between electronic states leads to a shift of the vibrational frequency during the excited-state evolution. In this regard, pump-degenerate four-wave mixing (pump-DFWM) is applied to a series of carotenoids with different numbers of conjugated double bonds N = 9, 10, 11 and 13 (neurosporene, spheroidene, lycopene and spirilloxanthin, respectively). Moreover, we demonstrate in a closed-chain carotenoid (lutein) that the coupling strength and therefore the vibrational shift can be tailored by changing the energy degeneracy between the 1B+u and 1B−u states via solvent interaction.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Cogdell, Professor Richard and Southall, Mrs June
Authors: Miki, T., Buckup, T., Krause, M. S., Southall, J., Cogdell, R. J., and Motzkus, M.
College/School:College of Medical Veterinary and Life Sciences > Institute of Molecular Cell and Systems Biology
Journal Name:Physical Chemistry Chemical Physics
Publisher:Royal Society of Chemistry
ISSN:1463-9076
ISSN (Online):1463-9084

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
502612Photosynthetic Antenna Research Center (PARC)Richard CogdellUS Department of Energy (DEN)DE-SC0001035RI MOLECULAR CELL & SYSTEMS BIOLOGY