Chromophore Localization in Conjugated Polymers:  Molecular Dynamics Simulation

Grimm, Stephan; Tabatabai, D; Scherer, A.; Michaelis, Jens; Frank, Irmgard

doi:10.1021/jp072032f

Cited by 14 publications

(13 citation statements)

References 45 publications

(90 reference statements)

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“…for example structural deviations from the PBC geometry, are likely to weaken or break the conjugation. 26 Moreover, it is good to keep in mind that the information is obtained only from the middle part of an infinitely long polymer, whereas the terminating ends and their effects can be assessed only from the oligomer models.…”

Section: Introductionmentioning

confidence: 99%

Modeling of photoactive conjugated donor–acceptor copolymers: the effect of the exact HF exchange in DFT functionals on geometries and gap energies of oligomer and periodic models

Niskanen

Hukka

2014

Phys. Chem. Chem. Phys.

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Conjugated copolymers with an alternating donor-acceptor (D-A) architecture are exploited as low-bandgap and high-hole-mobility materials in organic electronics. However, several of the presently available modeling methods predict different geometries and electronic properties for the same copolymer. In this work, the effect of the amount of exact Hartree-Fock (HF) exchange in density functionals on the planarity of the geometry and the electronic properties of the single oligomer chains of one benzodithiophene- and benzotriazole-based donor-acceptor copolymer and two fluorene-, thiophene-, and benzotriazole-based donor-acceptor copolymers is assessed. The functionals are B3LYP, PBE, PBE0, HSE06, LC-ωPBE, ωB97XD, M06, M06L, M062X, M06HF, and the optimally tuned OT-ωB97X. Benchmarking of the methods is useful for understanding the results of a particular functional and allows, to a certain degree, comparison between results obtained with different functionals. Additionally, the applicability of the one-dimensional periodic boundary condition (PBC) for modeling the D-A copolymers with long constitutional repeating units (CRUs) is evaluated.

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Section: Introductionmentioning

confidence: 99%

Modeling of photoactive conjugated donor–acceptor copolymers: the effect of the exact HF exchange in DFT functionals on geometries and gap energies of oligomer and periodic models

Niskanen

Hukka

2014

Phys. Chem. Chem. Phys.

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“…Our choice of the model system is motivated by the fact that alkyl side chains, attached to the thiophene monomers for increased solubility, cause a modest twist to the nominally planar polythiophene backbone. The degree of twisting modulates the strength of the inter-ring electronic couplings and affects directly the optoelectronic properties of the polymer, − making P3HT a convenient test-bed for structure–optoelectronic properties relationships. By tuning access to the strained conformations, using temperature as a proxy for more general perturbations, we explore how the various measures of torsional disorder impact optoelectronic properties and, in particular, affect the interplay between spatial delocalization and electron–hole polarization of excited states.…”

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confidence: 99%

Relating Chromophoric and Structural Disorder in Conjugated Polymers

Simine

Rossky

2017

J. Phys. Chem. Lett.

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The optoelectronic properties of amorphous conjugated polymers are sensitive to the details of the conformational disorder, and spectroscopy provides the means for structural characterization of the fragments of the chain that interact with light-"chromophores". A faithful interpretation of spectroscopic conformational signatures, however, presents a theoretical challenge. Here we investigate the relationship between the ground-state optical gaps, the properties of the excited states, and the structural features of chromophores of a single molecule poly(3-hexyl)-thiophene (P3HT) using quantum-classical atomistic simulations. Our results demonstrate that chromophoric disorder arises through the interplay between excited-state delocalization and electron-hole polarization, controlled by the torsional disorder introduced by side chains. Within this conceptual framework, we predict and explain the counterintuitive spectral behavior of P3HT, a red-shifted absorption, despite shortening of chromophores, with increasing temperature. This discussion introduces the concept of disorder-induced separation of charges in amorphous conjugated polymers.

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“…Torsional defects have been known to break the p electron delocalization in PPV 32 and other conjugated polymers. 33 The Fig.…”

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confidence: 99%

Spectral multitude and spectral dynamics reflect changing conjugation length in single molecules of oligophenylenevinylenes

Kobayashi

Tsuchiya

Oginö

et al. 2012

Phys. Chem. Chem. Phys.

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Single-molecule study of phenylenevinylene oligomers revealed distinct spectral forms due to different conjugation lengths which are determined by torsional defects. Large spectral jumps between different spectral forms were ascribed to torsional flips of a single phenylene ring. These spectral changes reflect the dynamic nature of electron delocalization in oligophenylenevinylenes and enable estimation of the phenylene torsional barriers.

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Chromophore Localization in Conjugated Polymers: Molecular Dynamics Simulation

Cited by 14 publications

References 45 publications

Modeling of photoactive conjugated donor–acceptor copolymers: the effect of the exact HF exchange in DFT functionals on geometries and gap energies of oligomer and periodic models

Modeling of photoactive conjugated donor–acceptor copolymers: the effect of the exact HF exchange in DFT functionals on geometries and gap energies of oligomer and periodic models

Relating Chromophoric and Structural Disorder in Conjugated Polymers

Spectral multitude and spectral dynamics reflect changing conjugation length in single molecules of oligophenylenevinylenes

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