Solvent polarity effect on excited‐state lifetime of carotenoids and some dyes

Pavlovich, V. S.

doi:10.1002/bip.20464

Cited by 11 publications

(8 citation statements)

References 27 publications

(39 reference statements)

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“…For comparison, one points out the long semiaxis of 13 Å employed in the ellipsoid cavity model. 25 Very low values of 4.5-5 Å 29 were based on the wrong assumption that the solvent effect is mainly originated from the lactone ring and partially from the polyene chain, while other parts of the peridinin molecule are untapped.…”

Section: Electric Dipole Moment At S 2 Excited State Effective Onsage...mentioning

confidence: 99%

“…The change of DMs during absorption, radiative and nonradiative transitions between electronic states is closely allied to the ICT dynamics. 13,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] However, at the moment, there is no clear consensus on both the CT nature of the excited states and on the DMs for peridinin. It should be also mentioned that there are a few reports 13,24,25 dealing with the calculations of peridinin intermolecular interactions in solutions.…”

Section: Introductionmentioning

confidence: 99%

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Gas-phase energy of the S2←S0 transition and electrostatic properties of the S2 state of carotenoid peridinin via a solvatochromic shift and orientation broadening of the absorption spectrum

Pavlovich

2014

Photochem Photobiol Sci

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The solvent effect on the position and the shape of the absorption spectrum of peridinin for 12 protic and aprotic solvents as well as the temperature effect for methanol were studied using a solvatochromic theory based on the Onsager sphere cavity model. (Experimental data have been provided by T. Polivka and V. Sundström.) Solvatochromic calculations combined with estimations of orientation broadening of the absorption spectrum by convolution allowed the conclusion that the orientation (dipole-dipole), induction and dispersion solute-solvent interactions reasonably describes the position of the 0-0 frequency. The orientation interactions led to the blue solvatochromic shift, separating them from the induced and dispersion interactions, which produce a red shift. The FWHM of Gaussian of inhomogeneous broadening originated from the fluctuations of orientation interactions was demonstrated to be high (945 cm(-1)) even for such a nonpolar solvent as hexane. The value of |Δμ|/cos φ of -18.7 D has been found (Δμ = μ2 - μg, φ is the angle between Δμ and μg). By assigning peridinin to the idealized C2v point group, the large change of dipole moment |Δμ| of 18.7 D under S2←S0 transition is obtained for peridinin in gas phase. Moreover, the S2-excited state dipole moment μ2 has the opposite orientation relative to that at the ground S0 state μg. The determined gas-phase 0-0 energy of the S2←S0 transition, 22 910 cm(-1) (2.84 eV) is employed to calculate the polarizability change between the S0 and S2 states of 376 Å(3). The finding for the effective Onsager radius is of 9.4 Å. Obtained results for electrostatic properties of the S2 state are compared with those known from Stark spectroscopy and quantum-mechanical calculations.

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Section: Electric Dipole Moment At S 2 Excited State Effective Onsage...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gas-phase energy of the S2←S0 transition and electrostatic properties of the S2 state of carotenoid peridinin via a solvatochromic shift and orientation broadening of the absorption spectrum

Pavlovich

2014

Photochem Photobiol Sci

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“…Schulten and Karplus pointed out the existence of a dark S 1 state in butadiene, and other dark intermediate states were identified by Tavan and Schulten in the context of longer polyenes . Since these theoretical studies, the notion of dark intermediates has been much debated in the experimental and theoretical literatureespecially in the context of radiationless relaxation. , These debates take on heightened complexity for carbonyl carotenoids, such as peridinin, that may exhibit photophysics indicative of intramolecular charge transfer (ICT). − Peridinin ICT is believed to stem from electron-rich allene and electron-withdrawing lactone functionalization. The ICT character in peridinin has been invoked to explain its unique photophysics distinguished by emission solvatochromism and Stark spectroscopy .…”

Section: Introductionmentioning

confidence: 99%

Peridinin Torsional Distortion and Bond-Length Alternation Introduce Intramolecular Charge-Transfer and Correlated Triplet Pair Intermediate Excited States

Taffet

Scholes

2018

J. Phys. Chem. B

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The nature of intramolecular charge transfer (ICT) and the mechanism of intramolecular singlet fission (SF) in peridinin remain open research questions. Obtaining an understanding of the population evolution from the bright state to dark state following a photoinduced electronic transition is critical. Unambiguously describing this evolution in peridinin, and light-harvesting carotenoids in general, has proven elusive experimentally and computationally. To offer a balanced description of the bright- and dark-state electronic structures, we here apply ab initio multireference perturbation theory quantum chemistry-the density matrix renormalization group self-consistent field and complete-active-space self-consistent field with second-order N-electron valence perturbation theory. At traditional bright- (S) and dark-state (S) optimized geometries, we find that an additional correlated triplet pair state and ICT state are derived from the canonical polyene B (S) and 3A (S) dark singlet excited states, respectively. Whereas the S state's physical properties are insensitive to peridinin's allene-tail donor and lactone ring acceptor functionalization, the S state exhibits a markedly enhanced oscillator strength and highest occupied molecular orbital-lowest unoccupied molecular orbital transition density. These changes suggest that the ICT character stems from mixing between the bright S and putatively dark S.

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“…Conclusively, the fluctuation the S 1 state seems to accelerate a fast nonradiative conversion of the S 1 state to a quenching state such as the T 1 state. 26 Roles of p-Aminophenyl and Pentafluorophenyl Substituents. We were initially curious why the photophysical properties of FFFF and AAAA are similar despite different intrinsic characters of p-aminophenyl and pentafluorophenyl substituents and why those of FFFA and FAFA are extraordinary.…”

Section: ■ Discussionmentioning

confidence: 99%

Characteristic Electronic Perturbation by Asymmetric Arrangements of p-Aminophenyl Substituents in Free-Base Porphyrins

et al. 2014

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We have investigated the perturbed electronic properties of meso-substituted free-base porphyrins with symmetric and asymmetric arrangements of substituents using time-resolved spectroscopic measurements and theoretical calculations. The extent of electronic perturbation by substituents in meso-substituted porphyrins is mainly affected by the isoenergetic condition of frontier MOs of porphine and substituent units, nonorthogonal geometry, and geometrical arrangement of substituents. By using the asymmetric arrangements of p-aminophenyl and pentafluorophenyl substituents, we can induce the electron-rich condition on the porphine unit and the intramolecular charge transfer character in the excited state. On the basis of this work, we can gain further insight into the energetic and geometric factors of substituents, the interaction between porphine and substituent units, and the perturbed photophysical and electronic properties by substituents, which provides a firm basis for further understanding of the catalytic activities or photophysical properties of porphyrins in porphyrin-based molecular catalysts and electronics.

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Solvent polarity effect on excited‐state lifetime of carotenoids and some dyes

Cited by 11 publications

References 27 publications

Gas-phase energy of the S2←S0 transition and electrostatic properties of the S2 state of carotenoid peridinin via a solvatochromic shift and orientation broadening of the absorption spectrum

Gas-phase energy of the S2←S0 transition and electrostatic properties of the S2 state of carotenoid peridinin via a solvatochromic shift and orientation broadening of the absorption spectrum

Peridinin Torsional Distortion and Bond-Length Alternation Introduce Intramolecular Charge-Transfer and Correlated Triplet Pair Intermediate Excited States

Characteristic Electronic Perturbation by Asymmetric Arrangements of p-Aminophenyl Substituents in Free-Base Porphyrins

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