Electronic absorption and ground state structure of carotenoid molecules
Journal of Physical Chemistry B, ISSN: 1520-6106, Vol: 117, Issue: 38, Page: 11015-11021
2013
- 93Citations
- 76Captures
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Metrics Details
- Citations93
- Citation Indexes93
- 93
- CrossRef85
- Captures76
- Readers76
- 76
Article Description
Predicting the complete electronic structure of carotenoid molecules remains an extremely complex problem, particularly in anisotropic media such as proteins. In this paper, we address the electronic properties of nine relatively simple carotenoids by the combined use of electronic absorption and resonance Raman spectroscopies. Linear carotenoids exhibit an excellent correlation between (i) the inverse of their conjugation chain length N, (ii) the energy of their S → S electronic transition, and (iii) the position of their ν Raman band (corresponding to the stretching mode of their conjugated C=C bonds). For cyclic carotenoids such as β-carotene, this correlation is also observed between the latter two parameters (S → S energy and ν frequency), whereas their "nominal" conjugation length N does not follow the same relationship. We conclude that β-carotene and cyclic carotenoids in general exhibit a shorter effective conjugation length than that expected from their chemical structure. In addition, the effect of solvent polarizability on these molecular parameters was investigated for four of the carotenoids used in this study. We demonstrate that resonance Raman spectroscopy can discriminate between the different effects underlying shifts in the S → S transition of carotenoid molecules. © 2013 American Chemical Society.
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