Quantum Molecular Dynamical Calculations of PEDOT 12-Oligomer and its Selenium and Tellurium Derivatives
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We present simulation results, computed with the Car–Parrinello molecular dynamics method, at zero and ambient temperature (300 K) for poly(3,4-ethylenedioxythiophene) [PEDOT] and its selenium and tellurium derivatives PEDOS and PEDOTe, represented as 12-oligomer chains. In particular, we focus on structural parameters such as the dihedral rotation angle distribution, as well as how the charge distribution is affected by temperature. We find that for PEDOT, the dihedral angle distribution shows two distinct local maxima whereas for PEDOS and PEDOTe, the distributions only have one clear maximum. The twisting stiffness at ambient temperature appears to be larger the lighter the heteroatom (S, Se, Te) is, in contrast to the case at 0 K. As regards point charge distributions, they suggest that aromaticity increases with temperature, and also that aromaticity becomes more pronounced the lighter the heteroatom is, both at 0 K and ambient temperature. Our results agree well with previous results, where available. The bond lengths are consistent with substantial aromatic character both at 0 K and at ambient temperature. Our calculations also reproduce the expected trend of diminishing gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital with increasing atomic number of the heteroatom.
KeywordsPEDOT PEDOS PEDOTe tellurium density functional theory dihedral angle
The authors acknowledge financial support from Vetenskapsrådet (VR), The Royal Swedish Academy of Sciences (KVA), the Knut and Alice Wallenberg Foundation (KAW), Carl Tryggers Stiftelse (CTS), Swedish Energy Agency (STEM), Swedish Foundation for Strategic Research (SSF), and Erasmus Mundus Action 2 TARGET II consortium. We are grateful to Prof. Mathieu Linares for interesting scientific discussions and valuable suggestions. The computations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC), Linköping University, the PDC Centre for High Performance Computing (PDC-HPC), KTH, and the High Performance Computing Center North (HPC2N), Umeå University.
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