The first detection of the 3A g − state in carotenoids using resonance-Raman excitation profiles

Furuichi, Kentaro; Sashima, Tokutake; Koyama, Yasushi

doi:10.1016/s0009-2614(02)00412-8

Cited by 102 publications

(101 citation statements)

References 19 publications

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“…[186,189,190] Additional experimental evidence for this state was obtained by stationary fluorescence [191] and resonance Raman spectroscopy. [179,182,192] The S* state was suggested to be either the 1B u À state [182,191,192] as predicted by Tavan and Schulten [177,193] or the 3A g À state. [179] In light-harvesting complexes, the S* state was proposed to be a 1B u À state which acts as precursor for triplet-state formation.…”

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confidence: 82%

“…[177] This indicates that a similar state ordering may occur in natural carotenoids (typically N = 7-13), which was supported by ultrafast spectroscopy [178] and resonance Raman excitation profiles. [179] The 1B u À state was proposed to be involved in the S 2 relaxation process of neurosporene via an internal conversion process…”

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confidence: 99%

“…This is supported by more recent MRCI calculations. [51] The 0-0 energies of the 1B u À and 3A g À states were determined by resonance Raman profiles for, for example, spheroidene to be at 2.18 eV (17 600 cm À1 ) [179,182] and at 2.48 eV (19 990 cm À1 ), [179] respectively. Another forbidden state in linear polyenes is the 1A g + state, which is also called the cis peak, because it becomes geometrically allowed in cis-polyenes due to their lack of inversion symmetry.…”

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confidence: 99%

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Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

2011

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The theoretical description of the initial steps in photosynthesis has gained increasing importance over the past few years. This is caused by more and more structural data becoming available for light-harvesting complexes and reaction centers which form the basis for atomistic calculations and by the progress made in the development of first-principles methods for excited electronic states of large molecules. In this Review, we discuss the advantages and pitfalls of theoretical methods applicable to photosynthetic pigments. Besides methodological aspects of excited-state electronic-structure methods, studies on chlorophyll-type and carotenoid-like molecules are discussed. We also address the concepts of exciton coupling and excitation-energy transfer (EET) and compare the different theoretical methods for the calculation of EET coupling constants. Applications to photosynthetic light-harvesting complexes and reaction centers based on such models are also analyzed.

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Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

2011

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“…Recent studies using resonance Raman excitation profiles and electronic absorption spectroscopy on substituted polyenes in the carotenoid family have indicated the presence of additional dark states below the 1B u + state. [68][69][70][71][72] In particular, for the all-trans-carotenoids with ͑the number of double bonds͒ n = 9 -11, Sashima et al 67 and Cerullo et al 73 72 The assignment was made by extrapolating from the earlier Pariser-ParrPople multi-reference doubles configuration interaction calculations by Tavan and Schulten on short polyenes ͑n =2-8͒, which had predicted the existence of these additional states. 56 To better understand the electronic structure of these low-lying states, we would ideally like to be able to carry out an ab initio multireference calculation using the complete -valence space.…”

Section: Introductionmentioning

confidence: 99%

Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene

Ghosh¹,

Hachmann²,

Yanai³

et al. 2008

The Journal of Chemical Physics

342

442

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In previous work we have shown that the density matrix renormalization group ͑DMRG͒ enables near-exact calculations in active spaces much larger than are possible with traditional complete active space algorithms. Here, we implement orbital optimization with the DMRG to further allow the self-consistent improvement of the active orbitals, as is done in the complete active space self-consistent field ͑CASSCF͒ method. We use our resulting DMRG-CASSCF method to study the low-lying excited states of the all-trans polyenes up to C 24 H 26 as well as ␤-carotene, correlating with near-exact accuracy the optimized complete -valence space with up to 24 active electrons and orbitals, and analyze our results in the light of the recent discovery from resonance Raman experiments of new optically dark states in the spectrum.

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“…An intermediate state with 1B u − symmetry (named S x ) mediating the S 2 → S 1 IC process has been first postulated theoretically and then experimentally demonstrated. [11][12][13][14][15][16][17][18][19][20] Recently, it has been proposed that when Cars are embedded in the LH2 complexes, S x might play an active role in the EET towards the higher excited state Q x of BChls. 21 Moreover, experimental evidence demonstrated the existence of another intermediate state, named S * , involved in the IC process of the Cars, whose origin and nature are still debated.…”

Section: Introductionmentioning

confidence: 99%

Ultra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium

Maiuri

Réhault

Carey

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inUltra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium We investigate the excitation energy transfer (EET) pathways in the photosynthetic light harvesting 1 (LH1) complex of purple bacterium Rhodospirillum rubrum with ultra-broadband two-dimensional electronic spectroscopy (2DES). We employ a 2DES apparatus in the partially collinear geometry, using a passive birefringent interferometer to generate the phase-locked pump pulse pair. This scheme easily lends itself to two-color operation, by coupling a sub-10 fs visible pulse with a sub-15-fs near-infrared pulse. This unique pulse combination allows us to simultaneously track with extremely high temporal resolution both the dynamics of the photoexcited carotenoid spirilloxanthin (Spx) in the visible range and the EET between the Spx and the B890 bacterio-chlorophyll (BChl), whose Q x and Q y transitions peak at 585 and 881 nm, respectively, in the near-infrared. Global analysis of the one-color and two-color 2DES maps unravels different relaxation mechanisms in the LH1 complex: (i) the initial events of the internal conversion process within the Spx, (ii) the parallel EET from the first bright state S 2 of the Spx towards the Q x state of the B890, and (iii) the internal conversion from Q x to Q y within the B890. C 2015 AIP Publishing LLC.[http://dx

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The first detection of the 3A g − state in carotenoids using resonance-Raman excitation profiles

Cited by 102 publications

References 19 publications

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene

Ultra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium

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