Electroabsorption spectroscopy of distyrylbenzene derivatives

Lane, Paul A.; Mellor, H.; Martin, Simon J.; Hagler, T.W.; Bleyer, A.; Bradley, Donal D. C.

doi:10.1016/s0301-0104(00)00146-4

Cited by 17 publications

(15 citation statements)

References 19 publications

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“…1 are listed in Table II together with the experimental data collected from both Stark spectroscopy 39,40 and FP-TRMC measurements. 5,19,21 The calculated results for shorter oligomers are shown to be in reasonable agreement with experimental data, especially when the experimental error margins are considered.…”

Section: Singlet B U Excitonsmentioning

confidence: 99%

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Grozema

Telesca

Jonkman

et al. 2001

The Journal of Chemical Physics

100

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In this paper, time-dependent density functional theory ͑TDDFT͒ calculations of excited state polarizabilities of conjugated molecules are presented. The increase in polarizability upon excitation was obtained by evaluating the dependence of the excitation energy on an applied static electric field. The excitation energy was found to vary quadratically with the field strength. The excess polarizabilities obtained for singlet excited states are in reasonable agreement with the experimental results for the shorter oligomers, particularly if the experimental uncertainties are considered. For longer oligomers the excess polarizability is considerably overestimated, similar to DFT calculations of ground state polarizabilities. Excess polarizabilities of triplet states were found to be smaller than those for the corresponding singlet state, which agrees with experimental results that are available for triplet polarizabilities. Negative polarizabilities are obtained for the lowest singlet A g states of longer oligomers. The polarizability of the lowest B u and A g excited states of the conjugated molecules studied here are determined mainly by the interaction between these two states. Upon application of a static electric field a quadratic Stark effect is observed in which the lower B u state has a positive excess polarizability and the upper A g state exhibits a decrease in polarizability upon excitation. All results are explained in terms of a sum-over-states description for the polarizability.

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Section: Singlet B U Excitonsmentioning

confidence: 99%

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Grozema

Telesca

Jonkman

et al. 2001

The Journal of Chemical Physics

100

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“…19,31 However, we have observed similar features in the EA spectra of distyrylbenzene derivatives where the central para-phenylene ring has been replaced by a meta-phenylene ring. 32 The EA spectrum is a weighted average of a number of phonons that couple to the electronic transition. It may be that the weighting function is different for meta-phenylene compounds than for paraphenylene compounds or that the change in the molecular symmetry changes which phonon modes couple to the electronic transition.…”

Section: Electronic Structure Of 13-ppvmentioning

confidence: 99%

Photophysics of a poly(phenylenevinylene) with alternatingmeta-phenylene andpara-phenylene rings

et al. 2000

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We have investigated the photophysics of the luminescent polymer poly͑1,3-phenylenevinylene-alt-2,5-dioctyloxy-1,4-phenylenevinylene͒ by a variety of optical spectroscopies. The incorporation of alternating meta-phenylene and para-phenylene rings restricts conjugation with respect to poly͑para-phenylenevinylene͒ derivatives. As a consequence, excited states are blueshifted and the nonlinear susceptibility is reduced. Absorption by aggregates, which can be obscured by scattering and interference, is clearly revealed by electroabsorption spectroscopy. The reduced symmetry of 1,3-PPV modifies optical selection rules, resulting in strong overlap of the fluorescence spectrum with excited state absorption by charged polarons.

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“…5 The large differences between these experimental values and the trends in them may be caused by differences in the surrounding medium. In the electroabsorption measurements by Lane et al, 14 measurements were performed in a solid PMMA matrix at 77 K, whereas in the FP-TRMC experiments by Gelinck et al the oligomers were studied in benzene solution at room temperature. 5 These very different environments can cause considerable differences in the geometry of the PV oligomer.…”

Section: B Methoxy Substituentsmentioning

confidence: 99%

“…For the third excited state, which dominates the absorption spectrum of meta-PV2, the calculated excess polarizability is rather low (88 Å 3 ) compared to that for PV2. This value can be compared to experimental data from electroabsorption measurements, 14 since in this technique the excess polarizability of excited states to which allowed transition exists is probed. An experimental value of 80 Å 3 was obtained from such measurements by Lane et al, 14 which is in good agreement with the calculated value.…”

Section: Meta-pv2mentioning

confidence: 99%

“…Similar observations have been made by Lane et al, who performed electroabsorption measurements. 14 Recently, it has been shown that the increase in polarizability upon excitation of a molecule ͑the excess polarizability, ⌬␣ ) can be obtained by calculating the optical absorption spectrum, using time-dependent density functional theory, as a function of an externally applied electric field. 15 For short conjugated molecules the method was found to give excess polarizabilities that are in good agreement with experimental data.…”

Section: Introductionmentioning

confidence: 99%

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Tuning of the excited state properties of phenylenevinylene oligomers: A time-dependent density functional theory study

Grozema

Telesca

Snijders

et al. 2003

The Journal of Chemical Physics

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This paper discusses a time-dependent density functional theory study of the effect of molecular structure on the excited state polarizability of conjugated molecules. A short phenylenevinylene oligomer containing three phenyl rings ͑PV2, distyryl benzene͒ is taken as a model system. Introduction of methyl substituents is shown to have only a small influence on the increase in polarizability upon excitation ͑the excess polarizability, ⌬␣ ). Methoxy groups have a much larger effect but in this case ⌬␣ depends strongly on the dihedral angle between the side chain and the backbone of the molecule. If the central phenyl ring of PV2 has a meta-configuration rather than para, both the optical absorption spectrum and the excess polarizability change considerably.

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Electroabsorption spectroscopy of distyrylbenzene derivatives

Cited by 17 publications

References 19 publications

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory

Photophysics of a poly(phenylenevinylene) with alternatingmeta-phenylene andpara-phenylene rings

Tuning of the excited state properties of phenylenevinylene oligomers: A time-dependent density functional theory study

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