Issue 26, 2017

Excited state characterization of carbonyl containing carotenoids: a comparison between single and multireference descriptions

Abstract

Carotenoids can play multiple roles in biological photoreceptors thanks to their rich photophysics. In the present work, we have investigated six of the most common carbonyl containing carotenoids: echinenone, canthaxanthin, astaxanthin, fucoxanthin, capsanthin and capsorubin. Their excitation properties are investigated by means of a hybrid density functional theory (DFT) and multireference configuration interaction (MRCI) approach to elucidate the role of the carbonyl group: the bright transition is of ππ* character, as expected, but the presence of a C[double bond, length as m-dash]O moiety reduces the energy of nπ* transitions which may become closer to the ππ* transition, in particular as the conjugation chain decreases. This can be related to the presence of a low-lying charge transfer state typical of short carbonyl-containing carotenoids. The DFT/MRCI results are finally used to benchmark single-reference time-dependent DFT-based methods: among the investigated functionals, the meta-GGA (and in particular M11L and MN12L) functionals show to perform the best for all six investigated systems.

Graphical abstract: Excited state characterization of carbonyl containing carotenoids: a comparison between single and multireference descriptions

Supplementary files

Article information

Article type
Paper
Submitted
04 May 2017
Accepted
15 Jun 2017
First published
15 Jun 2017

Phys. Chem. Chem. Phys., 2017,19, 17156-17166

Excited state characterization of carbonyl containing carotenoids: a comparison between single and multireference descriptions

R. Spezia, S. Knecht and B. Mennucci, Phys. Chem. Chem. Phys., 2017, 19, 17156 DOI: 10.1039/C7CP02941A

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