<i>Ab Initio</i>Calculation of the Electronic and Optical Excitations in Polythiophene: Effects of Intra- and Interchain Screening

Horst, J.W. van der; Bobbert, Peter A.; Michels, M.A.J.; Brocks, G.; Kelly, Paul J.

doi:10.1103/physrevlett.83.4413

Cited by 157 publications

(146 citation statements)

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“…In the present paper, we study the one-particle and two-particle excitations of PT and PPV in a crystalline geometry, replacing the effective dielectric environment in our previous calculations by the actual environment in the crystal. Furthermore, the crucial difference between the present calculations and our earlier work on PT 13,14 is that in the present calculations we do allow for wave-function overlap between adjacent chains.…”

Section: Introductionmentioning

confidence: 62%

“…15͒ and 0.6 eV, 16 respectively. We have demonstrated that by embedding a polythiophene chain in a medium with the appropriate frequency-dependent dielectric constants, the exciton binding energy is reduced to 0.76 eV, 13,14 while the optical gap remains virtually unaffected. A similar drastic reduction of the exciton binding energy by interchain screening effects was predicted earlier by Moore and Yaron 17 in polyacetylene, within the semiempirical Pariser-Parr-Pople theory.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, Green's function methods for the first-principles description of the electronic ͑one-particle͒ and optical ͑two-particle͒ excitations of extended systems have been developed and applied to several systems. [9][10][11] In the meantime, these methods have been applied to the conjugated polymers polyacetylene, 12 polyphenylenevinylene 12 ͑PPV͒, and polythiophene 13,14 ͑PT͒. For these three polymers calculations for an isolated polymer chain were performed, leading to a good agreement for the excitation energy of the lowest optically active singlet exciton, but a very large binding energy for this exciton.…”

Section: Introductionmentioning

confidence: 99%

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Electronic and optical excitations in crystalline conjugated polymers

2002

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We calculate the electronic and optical excitations of crystalline polythiophene and polyphenylenevinylene, using the GW approximation for the electronic self-energy and including excitonic effects by solving the electron-hole Bethe-Salpeter equation. We compare with our earlier calculations on an isolated polythiophene chain and polymer chains embedded in a dielectric medium. Surprisingly, we find for the crystalline calculations optical gaps and exciton binding energies that are significantly smaller than present experimental values. We attribute the disagreement to the fact that the quantum-mechanical coherence between polymer chains, present in the calculations, is absent in most experimental situations. We discuss possible reasons for this absence. Our general conclusion is that the picture of a polymer chain in a dielectric medium is most appropriate in describing the present experimental data on electronic and optical excitations in conjugated polymers.

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Section: Introductionmentioning

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electronic and optical excitations in crystalline conjugated polymers

2002

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“…In a recent paper, 17 hereafter referred to as I, we focused on the differences in excitations between an isolated polythiophene ͑PT͒ chain, see Fig. 1, and crystalline polythiophene.…”

Section: -7͔͒ Binding Energies Have Been Proposedmentioning

confidence: 99%

Ab initioprediction of the electronic and optical excitations in polythiophene: Isolated chains versus bulk polymer

et al. 2000

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initio prediction of the electronic and optical excitations in polythiophene : isolated chains versus bulk polymer. Physical Review B, 61(23), 15817-15826. DOI: 10.1103/PhysRevB.61.15817 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. We calculate the electronic and optical excitations of polythiophene using the GW ͑G stands for one-electron Green function, W for the screened Coulomb interaction͒ approximation for the electronic self-energy, and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. Two different situations are studied: excitations on isolated chains and excitations on chains in crystalline polythiophene. The dielectric tensor for the crystalline situation is obtained by modeling the polymer chains as polarizable line objects, with a long-wavelength polarizability tensor obtained from the ab initio polarizability function of the isolated chain. With this model dielectric tensor we construct a screened interaction for the crystalline case, including both intra-and interchain screening. In the crystalline situation both the quasiparticle band gap and the exciton binding energies are drastically reduced in comparison with the isolated chain. However, the optical gap is hardly affected. We expect this result to be relevant for conjugated polymers in general.

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“…It is well understood that, in general, both semi-empirical (such as AM1) and DFT methods provide reasonable geometries and ZINDO can deliver good UV-visible spectra for such molecular systems [14,15]. Even more accurate TD-DFT approaches are able to tackle complicated electronic features such as exciton binding energy [16,17,18] and double excitations [19]. Furthermore, based on the results of the calculations, absorption an emission spectra can be modeled, for example, for polyenes, oligoarylenes, phenylenevinylenes, and polyfluorenes [10,20,21].…”

Section: Introductionmentioning

confidence: 99%

A joint theoretical and experimental study of phenylene–acetylene molecular wires

Magyar

Tretiak

Gao

et al. 2005

Chemical Physics Letters

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The excited state electronic structure of π conjugated phenylene-acetylene oligomers is calculated using time-dependent density functional theory (TD-DFT) approaches. The theoretical fluorescence spectra are analyzed in terms of Frank-Condon active nuclear normal modes and shown to compare well with experiment. Theoretical and experimental results for the optical absorption and emission spectra of these molecules indicate that the conjugation length can be significantly reduced by conformational rotations about the triple-bonded carbon links. This has serious implications on the electronic functionalities of polyphenylene-acetylene based molecular wires and their possible use as charge/energy conduits in nano-assemblies.

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Ab InitioCalculation of the Electronic and Optical Excitations in Polythiophene: Effects of Intra- and Interchain Screening

Cited by 157 publications

References 24 publications

Electronic and optical excitations in crystalline conjugated polymers

Electronic and optical excitations in crystalline conjugated polymers

Ab initioprediction of the electronic and optical excitations in polythiophene: Isolated chains versus bulk polymer

A joint theoretical and experimental study of phenylene–acetylene molecular wires

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