Quantitative interpretation of the absorption and emission spectra of 1,8-diphenyl-1,3,5,7-octatetraene

Henneker, W. H.; Siebrand, Willem; Zgierski, Marek Z.

doi:10.1063/1.446091

Cited by 26 publications

(12 citation statements)

References 7 publications

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“…Dceyama and Azumi propose that the anomalous fluorescence behavior of DPO is only partially accounted for by Herzberg-Teller vibronic coupling of Sj and S2 and that the molecule may be distorted somewhat from the symmetry of the C^, point group.58 A more accurate treatment of the coupling, involving direct diagonalization of the appropriate Hamiltonian matrix, has since been proposed. 59 Studies of the effects of solvents and substituents on the fluorescence and isomerization behavior of diphenylpolyenes complement such calculations and, as discussed in the following sections, have revealed much about the nature of barriers, curve crossing, and isomerization dynamics.…”

Section: Excited Electronic Statesmentioning

confidence: 97%

The photophysics and photochemistry of .alpha.,.omega.-diphenylpolyene singlet states

Allen¹,

Whitten²

1989

Chem. Rev.

183

141

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Section: Excited Electronic Statesmentioning

confidence: 97%

The photophysics and photochemistry of .alpha.,.omega.-diphenylpolyene singlet states

Allen¹,

Whitten²

1989

Chem. Rev.

183

141

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“…This is at variance with smaller values of the displacement for the S mode reported for DPOT and other polyenes. 3,7,20 We explain this difference primarily by the model considered here. With the linewidths, which increase with the quantum number for the S mode, a larger potential displacement is required to fit the peak heights of the observed S-mode transitions.…”

Section: S 1 -S 2 Coupling Strength and Potential Displacementsmentioning

confidence: 99%

“…20,18 This model allows for an easy parametrization of the observations in terms of harmonic vibrational modes. The part of the coupling that generates irregularities in the vibronic frequency and intensity progressions is considered by a Hamiltonian in the basis of nonadiabatic vibronic states.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13][14][15][16][17][18][19][20][21][22] In the vacuum this is due to the Herzberg-Teller ͑HT͒ coupling of the S 1 and S 2 states via the distortion of the molecular configuration through promoting vibrational modes of u symmetry. 11,23,24 Accordingly the S 1 -S 0 spectra start at 1-0 origins of HT promoting modes and the vibrational progressions are combinations of promoting and Franck-Condon active modes.…”

Section: Introductionmentioning

confidence: 99%

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Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

Walser

Zumofen

Plakhotnik

2000

The Journal of Chemical Physics

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Articles you may be interested inElectronic spectra of azaindole and its excited state mixing: A symmetry-adapted cluster configuration interaction study J. Chem. Phys. 143, 204304 (2015); 10.1063/1.4935578The elusive S 2 state, the S 1/S 2 splitting, and the excimer states of the benzene dimer J. Chem. Phys. 142, 234306 (2015) One-and two-photon excitation spectra, as well as absorption and emission spectra of diphenyloctatetraene ͑DPOT͒ in n-alkanes are investigated at low temperatures. For DPOT in n-octane we report on the measurements of one-photon excitation and emission spectra and for DPOT in n-tetradecane ͑TD͒ on the measurements of one-and two-photon excitation spectra and emission spectra. The spectra are governed by the transitions between the electronic ground (S 0 ) and the two lowest electronic excited singlet states (S 1 ,S 2 ). The interpretation is based on allowed transitions and transitions induced by the S 1 -S 2 coupling due to Herzberg-Teller promoting modes or due to static lattice-induced distortions of DPOT. A single noncentrosymmetric site is observed for DPOT in n-octane. For DPOT in TD a centrosymmetric and a noncentrosymmetric site are reported. The analysis indicates that there is a dynamical equilibrium in the population of these two sites. The experimental data are quantitatively studied by comparison with simulated spectra. The simulation calculations are based on the coupling between nonadiabatic S 1 and S 2 states, harmonic modes, and suitable transition moments and line-shape functions. For DPOT in TD the calculations reveal an interesting interference pattern in the vibronic progressions observed in two-photon excitation spectra.

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“…By investigating a series of diphenyl polyenes (n = 2, 3,4), Hudson and Kohler have shown [3,4] for all-transdiphenyl-1,3,5,7-octatetraene (n = 4) (DPO), that the lowest excited singlet state is the optically forbidden 2 1 A g (S 1 ) state which lines below the optically allowed 1 1 B U (S 2 ) state. The 2*A g <-1 1 A g transition is lower in energy [1,2] and gains intensity from the l^ <-l*A g transition by vibronic coupling [5,6], For all diphenyl polyenes, n = 2, 3, 4, the transition moment is parallel to the long molecular axis [7,8].…”

Section: Introductionmentioning

confidence: 99%

Isomerization of Diphenyl Polyenes. Part VI. Properties of l,8-Diphenyl-l,3,5,7-octatetraene Fluorescence in Poly (vinyl alcohol) and other Polymer Films

Kawski

Kubicki

Kukliński

et al. 1993

Zeitschrift Für Naturforschung A

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Absorption, fluorescence and emission anisotropy spectra of l,8-diphenyl-l,3,5,7-octatetraene (DPO) in non-heated and heated polyvinyl alcohol) (PVA) films were measured at 296 and 87 K. Similar spectra to those of DPO in PVA heated to 423 K were observed for DPO in polymer films: polyvinyl chloride) (PVCh), polyvinyl formal) (PVF) and ethylacetate (EtA). Unusual photophysical properties of DPO fluorescence occur only in non-heated PVA. These are the increase in the absorbance and quantum yield at temperatures above 358 K and the change in the emission anisotropy, r, due to softening or stiffening of the PVA film. For DPO in PVCh and EtA, high values of r, close to 0.4, are observed (0.391 and 0.389, respectively), thus manifesting the stiffening of the microenvironment around the DPO molecule in these polymers. In the case of DPO in non-heated PVA film, strong temperature dependence of the intensity distribution in the fluorescence band and double exponential emission decay are observed. This proves that the fluorescence originates from two conformers: all-trans and s-eis.

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Quantitative interpretation of the absorption and emission spectra of 1,8-diphenyl-1,3,5,7-octatetraene

Abstract: Diagonalization of two-state, two-mode Hamiltonian matrix accounts quantitatively for the absorption and emission spectra of 1,8-diphenyl-1,3,5,7-octatetraene observed by Ikeyama and Azumi [J. Chem. Phys. 76, 5762 (1982)].

Cited by 26 publications

References 7 publications

The photophysics and photochemistry of .alpha.,.omega.-diphenylpolyene singlet states

The photophysics and photochemistry of .alpha.,.omega.-diphenylpolyene singlet states

Symmetry breaking and spectra of diphenyloctatetraene in n-alkanes

Isomerization of Diphenyl Polyenes. Part VI. Properties of l,8-Diphenyl-l,3,5,7-octatetraene Fluorescence in Poly (vinyl alcohol) and other Polymer Films

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