Low-lying singlet states of carotenoids having 8–13 conjugated double bonds as determined by electronic absorption spectroscopy

Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Haruki; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jianping

doi:10.1016/j.cplett.2005.05.037

Cited by 34 publications

(63 citation statements)

References 12 publications

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“…According to our best estimates (see Fig. 10(a)) this switch occurs near N = 14, which is in close agreement with the spectroscopic data of Snyder et al 36 and Wang et al 37 discussed in the Introduction.…”

Section: Discussionsupporting

confidence: 80%

“…According to these calculations the vertical transition to the 1B − u state appears below the 1B + u transition at N ≥ 14 and the transition to the 3A − g state at N ≥ 22. In the carotenoids the latter state switch is observed for the 0-0 transitions at N ≥ 20, 37 while the early PPP/MRCI treatment yielded an extrapolated switch at N ≥ 20.…”

Section: Quantum Chemical Descriptions Of Polyene Spectramentioning

confidence: 95%

“…They attributed a fluorescence newly appearing at N = 14 energetically a little below the onset of the 1B + u absorption to this state despite the 370 cm −1 Stokes shift and the lack of symmetry between the absorption and emission spectrum, both of which are easily rationalized in terms of another electronic state (1B − u ) slightly below the 1B + u state. According to Wang et al 37 the 1B − u state appears below the 1B + u state in the carotenoids for N > 14, i.e., at a size very close to that of the pure polyene studied in Ref. 36.…”

Section: B Development Of Polyene Spectroscopymentioning

confidence: 99%

“…12) provides in Table S4 experimental (gas phase) polyene excitation energies constructed and compiled by us from many sources available in the literature. [36][37][38][39][40][41][42] Additionally, these data are graphically represented in the accompanying Figs. S15 and S16.…”

Section: B Development Of Polyene Spectroscopymentioning

confidence: 99%

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Electronic excitations in long polyenes revisited

Schmidt

Tavan

2012

The Journal of Chemical Physics

106

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We apply the valence shell model OM2 [W. Weber and W. Thiel, Theor. Chem. Acc. 103, 495, (2000)] combined with multireference configuration interaction (MRCI) to compute the vertical excitation energies and transition dipole moments of the low-energy singlet excitations in the polyenes with 4 ≤ N ≤ 22π -electrons. We find that the OM2/MRCI descriptions closely resemble those of Pariser-Parr-Pople (PPP) π -electron models [P. Tavan and K. Schulten, Phys. Rev. B 36, 4337, (1987)], if equivalent MRCI procedures and regularly alternating model geometries are used. OM2/MRCI optimized geometries are shown to entail improved descriptions particularly for smaller polyenes (N ≤ 12), for which sizeable deviations from the regular model geometries are found. With configuration interaction active spaces covering also the σ -in addition to the π -electrons, OM2/MRCI excitation energies turn out to become smaller by at most 0.35 eV for the ionic and 0.15 eV for the covalent excitations. The particle-hole (ph) symmetry, which in Pariser-Parr-Pople models arises from the zero-differential overlap approximation, is demonstrated to be only weakly broken in OM2 such that the oscillator strengths of the covalent 1B − u states, which artificially vanish in ph-symmetric models, are predicted to be very small. According to OM2/MRCI and experimental data the 1B − u state is the third excited singlet state for N < 12 and becomes the second for N ≥ 14. By comparisons with results of other theoretical approaches and experimental evidence we argue that deficiencies of the particular MRCI method employed by us, which show up in a poor size consistency of the covalent excitations for N > 12, are caused by its restriction to at most doubly excited references.

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Section: Discussionsupporting

confidence: 80%

Section: Quantum Chemical Descriptions Of Polyene Spectramentioning

confidence: 95%

Section: B Development Of Polyene Spectroscopymentioning

confidence: 99%

Section: B Development Of Polyene Spectroscopymentioning

confidence: 99%

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Electronic excitations in long polyenes revisited

Schmidt

Tavan

2012

The Journal of Chemical Physics

106

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“…However, predicting the full electronic structure of Car molecules has turned out to be extremely complex. Despite the intense level of research on Car properties over the last 40 years, several new, low energy excited states have been proposed for these molecules in the last decade alone (23,24), and precise calculations of their electronic and vibrational properties still remain a challenge (25). In vivo, protein binding sites provide a highly anisotropic environment to Car molecules.…”

mentioning

confidence: 99%

Mechanisms Underlying Carotenoid Absorption in Oxygenic Photosynthetic Proteins

Mendes-Pinto

Galzerano

Telfer

et al. 2013

Journal of Biological Chemistry

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Background: Tuning of carotenoid function, through modulation of their electronic properties, is seen throughout Nature. Results: Two photosynthetic proteins are able to modulate the effective conjugation length of bound carotenoid cofactors. Conclusion: Altering the conformation of conjugated end cycles via steric hindrance provides a means of tuning the electronic properties of carotenoids. Significance: A novel mechanism tuning the functional properties of carotenoids is revealed.

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Mechanisms of Carotenoid-to-Bacteriochlorophyll Energy Transfer in the Light Harvesting Antenna Complexes 1 and 2: Dependence on the Conjugation Length of Carotenoids

Koyama

Kakitani

Advances in Photosynthesis and Respiration

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Low-lying singlet states of carotenoids having 8–13 conjugated double bonds as determined by electronic absorption spectroscopy

Cited by 34 publications

References 12 publications

Electronic excitations in long polyenes revisited

Electronic excitations in long polyenes revisited

Mechanisms Underlying Carotenoid Absorption in Oxygenic Photosynthetic Proteins

Mechanisms of Carotenoid-to-Bacteriochlorophyll Energy Transfer in the Light Harvesting Antenna Complexes 1 and 2: Dependence on the Conjugation Length of Carotenoids

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