Excited-state dynamics of the 1Bu+,3Ag−, and 1Bu− states in a carotenoid molecule by 5-fs absorption spectroscopy

Kobayashi, Takayoshi; Nishimura, Kohei; Rondonuwu, Ferdy S.; Koyama, Yasushi

doi:10.1016/j.jlumin.2004.09.030

Cited by 4 publications

(3 citation statements)

References 13 publications

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“…Ultrafast time-resolved transient absorption spectroscopic experiments carried out by Zhang et al and Cerullo et al suggested that a dark intermediate state, termed S x , which was needed to account for their observations, was possibly the 1 1 B u – state populated during the decay between S 2 and S 1 for carotenoids having N ≥ 9. Indeed, the assignment of the dark intermediate state to a 1 1 B u – state would be consistent with the computational models for polyenes advanced by Tavan and Schulten, and additional quantum mechanical calculations support this view. ,,,− Also, spectroscopic bands in the near-IR (800–950 nm) − or visible (∼600 nm) − regions of the transient absorption spectra for various carotenoids were assigned to the 1 1 B u – state in subsequent reports. More recently, Ostroumov et al , employed two-dimensional electronic spectroscopy and argued that the S x state is the 1 1 B u – state and that it electronically couples with both the 1 1 B u + state of the carotenoid and the Q x band of bacteriochlorophyll via the Herzberg–Teller mechanism. − …”

Section: Introductionsupporting

confidence: 78%

The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues

et al. 2017

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Theoretical studies have predicted the presence of a forbidden 1B state in proximity to the strongly allowed 1B excited state in polyenes and carotenoids. The 1B state is invariably predicted to have a very low oscillator strength, which precludes direct optical spectroscopic assignment. We report here a direct UV-vis optical spectroscopic feature assigned to the 1B state of S-2-peridinin, a synthetic analogue of the naturally occurring carotenoid, peridinin. The shift of the ground state dipole of S-2-peridinin compared to natural peridinin enhances the oscillator strength of absorption from the ground state to the 1B state by 2 orders of magnitude relative to peridinin. It is postulated that this is due to a quadrupolar electrostatic field generated from the more central location of the lactone ring along the polyene chain in S-2-peridinin. MNDO-PSDCI and EOM-CCSD calculations provide a theoretical basis for this assignment and explain the unique properties of the 1B state and why the transition from the ground state to this state has such a low oscillator strength in most other polyenes and carotenoids.

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Section: Introductionsupporting

confidence: 78%

The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues

et al. 2017

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“…Computational excited-state conjugation-length trends, however, have not been met with unambiguous spectroscopic support. For instance, the photoinduced absorption peaks attributed to a dark intermediate state do not appear to increase in excitation energy with increasing conjugation lengthan apparent contradiction. ,− Moreover, advanced techniques recently used − to study carotenoid internal conversion hint at complexities not revealed by earlier transient absorption spectroscopy studies . As a result, conflict exists between early experimental descriptions of a “hot” lowest-lying dark state , mediating population transfer to the lowest-lying excited-state equilibrium geometry and later hypotheses of a bridging dark intermediate state. ,,,,, …”

Section: Introductionmentioning

confidence: 99%

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

et al. 2019

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We report quantum chemical calculations using multireference perturbation theory (MRPT) with the density matrix renormalization group (DMRG) plus photothermal deflection spectroscopy measurements to investigate the manifold of carotenoid excited states and establish their energies relative to the bright state (S 2 ) as a function of nuclear reorganization. We conclude that the primary photophysics and function of carotenoids are determined by interplay of only the bright (S 2 ) and lowest-energy dark (S 1 ) states. The lowest-lying dark state, far from being energetically distinguishable from the lowest-lying bright state along the entire excited-state nuclear reorganization pathway, is instead computed to be either the second or first excited state depending on what equilibrium geometry is considered. This result suggests that, rather than there being a dark intermediate excited state bridging a non-negligible energy gap from the lowestlying dark state to the lowest-lying bright state, there is in fact no appreciable energy gap to bridge following photoexcitation. Instead, excited-state nuclear reorganization constitutes the bridge from S 2 to S 1 , in the sense that these two states attain energetic degeneracy along this pathway.

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“…[3,4] In particular, these luminescent lanthanide complexes are used as fluorescence probes for analytical applications due to their unique luminescence characteristics, such as narrow spectral width, long luminescence lifetime and large Stokes shift. [5–9] Recently, there has been an increased interest in exploration of the structure functions of bimolecular reactions with lanthanide complexes. [10,11]…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and fluorescent properties of cerium(III) glutathione complex

Han¹,

Liu²

2009

Luminescence

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The cerium (III) glutathione complex was synthesized by the redox reaction of cerium (IV) with glutathione reduced (GSH) in aqueous solution. The Job-plots indicate an ML (L = GSSG) stoichiometry of the complex. The fluorescent properties of the compound were investigated. The as-prepared complex showed the characteristic maximum emission spectra of Ce(III) at 350 nm (λ(ex) = 255 nm). The fluorescence results show that the Ce(IV) ions are first reduced to Ce(III), and then form Ce(III) complex after reacting with GSH. The complex was characterized by element analysis and FT-IR spectra; the stability of the complex was analyzed by cyclic voltammeters and DSC-TG as well. Finally, Ce(IV) was successfully employed to determine the concentrations of GSH in the presence of GSSG, in which the fluorescence intensities are proportional to the concentrations of GSH in the range of 1-100 nM with the detection limit of 0.05 nM of GSH, without interference from the presence of GSSG.

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Excited-state dynamics of the 1Bu+,3Ag−, and 1Bu− states in a carotenoid molecule by 5-fs absorption spectroscopy

Cited by 4 publications

References 13 publications

The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues

The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Synthesis, characterization and fluorescent properties of cerium(III) glutathione complex

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Excited-state dynamics of the 1Bu+,3Ag−, and 1Bu− states in a carotenoid molecule by 5-fs absorption spectroscopy

Cited by 4 publications

References 13 publications

The Forbidden 11Bu– Excited Singlet State in Peridinin and Peridinin Analogues

The Forbidden 11Bu– Excited Singlet State in Peridinin and Peridinin Analogues

Carotenoid Nuclear Reorganization and Interplay of Bright and Dark Excited States

Synthesis, characterization and fluorescent properties of cerium(III) glutathione complex

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Product

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The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues

The Forbidden 1¹B_u^– Excited Singlet State in Peridinin and Peridinin Analogues