Vibronic coupling in the excited-states of carotenoids

Miki, Takeshi; Buckup, Tiago; Krause, Marie S.; Southall, June; Cogdell, Richard J.; Motzkus, Marcus

doi:10.1039/C5CP07542D

Vibronic coupling in the excited-states of carotenoids

Journal Article · Wed Mar 23 00:00:00 EDT 2016 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C5CP07542D· OSTI ID:1387730

Miki, Takeshi ^[1]; Buckup, Tiago ^[1]; Krause, Marie S. ^[1]; Southall, June ^[2]; Cogdell, Richard J. ^[2]; Motzkus, Marcus ^[1]

Ruprecht-Karls-Universität Heidelberg (Germany)
Univ. of Glasgow, Scotland (United Kingdom)

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$$^–_\text{g}$$ and 1B$$^–_\text{u}$$) 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. In this work, 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$$^+_\text{u}$$ and 1B$$^–_\text{u}$$ states via solvent interaction.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001035

OSTI ID:: 1387730

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 16 Vol. 18; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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