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Excited-state modeling of the astaxanthin dimer predicts a minor contribution from exciton coupling to the bathochromic shift in crustacyanin
University of Siena, Italy .
Uppsala University, Sweden.
2009 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 113, no 15, 5311-5317 p.Article in journal (Refereed) Published
Abstract [en]

The >0.50 eV bathochromic shift of the absorption by the carotenoid astaxanthin in crustacyanin, the carotenoprotein responsible for the coloration of lobster shell, is believed to result from ground-state polarization of the chromophore and/or exciton coupling between the two chromophores of each protein subunit. Here, the contribution of exciton coupling to the shift is quantified using quantum chemical calculations that do not rely on the dipole-dipole approximation but rather consider the full astaxanthin dimer in the geometry relevant for the protein-bound state. Employing a variety of methods, it is found that the exciton coupling amounts to 0.04 eV only. Furthermore, even when more closely aggregated dimers than the one in the protein are considered, the predicted couplings remain small (0.05-0.09 eV). These findings demonstrate that the bathochromic shift cannot be explained in terms of exciton coupling. It is therefore argued that polarization is likely to be the dominant mechanism, a notion supported by the fact that calculations carried out at the same levels of theory identify a scenario (hydrogen bonding with a histidine residue) whose contribution to the shift vastly exceeds that of exciton coupling.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2009. Vol. 113, no 15, 5311-5317 p.
National Category
Natural Sciences
URN: urn:nbn:se:liu:diva-96735DOI: 10.1021/jp810754sOAI: diva2:643065
Available from: 2013-08-26 Created: 2013-08-26 Last updated: 2013-09-02Bibliographically approved

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Durbeej, Bo
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