Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis

Qu, Guannan; Xin, Minsi; Jia, Qiang; Cai, Pengcheng; Jin, Guangyong; Zhou, Yunquan; Liu, Chunyu; Tan, Yidong; Zhang, Ye; Yao, Zhihai; Feng, Aoran; Cai, Huaqiang

doi:10.1016/j.ijleo.2019.03.109

Cited by 6 publications

(2 citation statements)

References 34 publications

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“…This effect can be attributed to constriction of a solvent cavity around the β-carotene chromophore in the ground state as the temperature decreases in the dark prior to illumination. The shift of the absorption spectrum to the red as the temperature is lowered arises from the temperature dependence of the solvent polarizability. ,,, …”

Section: Resultssupporting

confidence: 82%

“…The shift of the absorption spectrum to the red as the temperature is lowered arises from the temperature dependence of the solvent polarizability. 8,16,85,86 The main result from Figure 7, however, is that the integrated oscillator strength of the fluorescence emission from β-carotene with 430 nm excitation markedly increases as the temperature is lowered due to a new contribution to the emission spectrum from a short-lived spectral "intermediate" along the S 2 to S 1 nonradiative decay pathway. The fluorescence oscillator strength spectra are shown with absolute scaling in Figure 7 to make clear how much stronger the emission is at 80 K; the quantum yield determined from the integrated oscillator strength is 78 times larger at 80 K, 1.5 × 10 −4 , than that at room temperature, 2.0 × 10 −6 .…”

Section: ■ Introductionsupporting

confidence: 82%

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Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene

et al. 2020

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Carotenoids are usually only weakly fluorescent despite being very strong absorbers in the mid-visible region because their first two excited singlet states, S 1 and S 2 , have very short lifetimes. To probe the structural mechanisms that promote the nonradiative decay of the S 2 state to the S 1 state, we have carried out a series of fluorescence lineshape and anisotropy measurements with a prototype carotenoid, β-carotene, in four aprotic solvents. The anisotropy values observed in the fluorescence emission bands originating from the S 2 and S 1 states reveal that the large internal rotations of the emission transition dipole moment, as much as 50°relative to that of the absorption transition dipole moment, are initiated during ultrafast evolution on the S 2 state potential energy surface and persist upon nonradiative decay to the S 1 state. Electronic structure calculations of the orientation of the transition dipole moment account for the anisotropy results in terms of torsional and pyramidal distortions near the center of the isoprenoid backbone. The excitation wavelength dependence of the fluorescence anisotropy indicates that these out-of-plane conformational motions are initiated by passage over a low-activation energy barrier from the Franck−Condon S 2 structure. This conclusion is consistent with detection over the 80−200 K range of a broad, red-shifted fluorescence band from a dynamic intermediate evolving on a steep gradient of the S 2 state potential energy surface after crossing the activation barrier. The temperature dependence of the oscillator strength and anisotropy indicate that nonadiabatic passage from S 2 through a conical intersection seam to S 1 is promoted by the out-of-plane motions of the isoprenoid backbone with strong hindrance by solvent friction.

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Section: Resultssupporting

confidence: 82%

Section: ■ Introductionsupporting

confidence: 82%

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene

et al. 2020

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Phase transition induced changes in β-ring rotation and methyl group asymmetric deformation of all-trans-β-carotene

Xin

Rasheed

et al. 2019

Journal of Molecular Liquids

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Effect of temperature on Electron-Phonon coupling of carotenoids by Two-Dimensional correlation resonance Raman spectroscopy

Chen

Zhao

et al. 2022

Journal of Molecular Liquids

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Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis

Cited by 6 publications

References 34 publications

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene

Phase transition induced changes in β-ring rotation and methyl group asymmetric deformation of all-trans-β-carotene

Effect of temperature on Electron-Phonon coupling of carotenoids by Two-Dimensional correlation resonance Raman spectroscopy

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Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis

Cited by 6 publications

References 34 publications

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S2 State of β-Carotene

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S2 State of β-Carotene

Phase transition induced changes in β-ring rotation and methyl group asymmetric deformation of all-trans-β-carotene

Effect of temperature on Electron-Phonon coupling of carotenoids by Two-Dimensional correlation resonance Raman spectroscopy

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Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene

Fluorescence Anisotropy Detection of Barrier Crossing and Ultrafast Conformational Dynamics in the S₂ State of β-Carotene