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Temperature dependence of band gaps and conformational disorder in PEDOT and its selenium and tellurium derivatives: density functional calculations
KTH, School of Engineering Sciences (SCI), Applied Physics.ORCID iD: 0000-0001-9970-5710
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. KTH, Centres, SeRC - Swedish e-Science Research Centre.ORCID iD: 0000-0002-9720-5429
KTH, Centres, SeRC - Swedish e-Science Research Centre. KTH, School of Engineering Sciences (SCI), Applied Physics. 5)Department of Physics and Astronomy, Materials Theory Division, Uppsala University.
2017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690Article in journal (Refereed) Published
Abstract [en]

The conducting polymer poly(3,4-ethylenedioxythiophene), or PEDOT, is an attractive material for flexibleelectronics. We present combined molecular dynamics and quantum chemical calculations, based on den-sity functional theory, of EDOT oligomers and isoelectronic selenium and tellurium derivatives (EDOS andEDOTe) to address the effect of temperature on the geometrical and electronic properties of these systems.With finite size scaling, we also extrapolate our results to the infinite polymers, i.e. PEDOT, PEDOS and PEDOTe. Our computations indicate that the most favourable oligomer conformations at finite temperature are conformations around the flat trans-conformation and a non-flat conformation around 45 from the cis-conformation. Also, the dihedral stiffness increases with the atomic number of the heteroatom. We find excellent agreement with experimentally measured gaps for PEDOT and PEDOS. For PEDOT, the gap does not increase with temperature where as this is the case for its derivatives. The conformational disorder as well as the choice of basis set both significantly affect the calculated gaps.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2017.
Keywords [en]
PEDOT, selenium, tellurium, density functional theory, Car-Parrinello molecular dynamics
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-214934DOI: 10.1063/1.4998509ISI: 000412321600030Scopus ID: 2-s2.0-85031789300OAI: oai:DiVA.org:kth-214934DiVA, id: diva2:1144228
Note

QC 20170928

Available from: 2017-09-25 Created: 2017-09-25 Last updated: 2017-11-15Bibliographically approved
In thesis
1. Electronic and optical properties of conducting polymers from quantum mechanical computations
Open this publication in new window or tab >>Electronic and optical properties of conducting polymers from quantum mechanical computations
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

    Conductive polymers are also known as "organic metals" due to their semiconducting properties. They are found in a wide range of applications in the field of organic electronics. However, the growing number of experimental works is not widely supported with theoretical calculations. Hence, the field of conductive polymers is experiencing lack of understanding of mechanisms occurring in the polymers. In this PhD thesis, the aim is to increase understanding of conductive polymers by performing theoretical calculations.       

The polymers poly(3,4-ethylenedioxythiophene) (PEDOT) together with its selenium (PEDOS) and tellurium (PEDOTe) derivatives, poly(p-phenylene) (PPP) and naphthobischalcogenadiazoles (NXz) were studied. Several computational methods were applied for analysis of mentioned structures, including density functional theory (DFT), tight-binding modelling (TB), and Car-Parrinello molecular dynamics (CPMD) calculations. The combination of CPMD and DFT calculations was applied to investigate the PEDOT, PEDOS and PEDOTe. The polymers were studied using four different functionals in order to investigate the full picture of structural changes, electronic and optical properties. Temperature effects were studied using molecular dynamics simulations. Wide statistics for structural and molecular orbitals analysis were collected.        

The TB method was employed for PPP. The formation and motion of the excitations, polarons and bipolarons, along the polymer backbone was investigated in presence of electric and magnetic fields. The influence of non-magnetic and magnetic impurities was determined.       

The extended π-conjugated structures of NXz were computed using B3LYP and ωB97XD functionals in combination with the 6-31+G(d) basis set. Here, the structural changes caused by polaron formation were analyzed. The combined analysis of densities of states and absorption spectra was used for understanding of the charge transition.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2017. p. 54
Series
TRITA-FYS, ISSN 0280-316X ; 2017:59
Keywords
density functional theory, DFT, Car-Parrinello molecular dynamics, CPMD, tigh-binding, poly(3, 4-ethylenedioxythiophene), PEDOT, selenium, PEDOS, tellurium, PEDOTe, poly(p-phenylene), poly(para-phenylene), poly(1, 4-phenylene), naphthobischalcogenadiazoles
National Category
Condensed Matter Physics Polymer Chemistry
Research subject
Physics
Identifiers
urn:nbn:se:kth:diva-214979 (URN)978-91-7729-529-7 (ISBN)
Public defence
2017-10-27, Sal C, Kistagången 16, Kista, 10:00 (English)
Opponent
Supervisors
Note

QC 20170928

Available from: 2017-09-28 Created: 2017-09-27 Last updated: 2017-09-28Bibliographically approved

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