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Item Electronic Structures and Optical Properties of p-Type/n-Type Polymer Blends: Density Functional Theory Study(ACS, 2020-04) Ghosh, SarbaniA blend made of p-type and n-type polymers can act as bipolar/ambipolar material composites that transport both electrons and holes. Although several experimental efforts are currently devoted to p-/n-type blends of conducting polymers, theoretical studies of these systems are missing to a large extent. In the current paper, using the density functional theory (DFT) and the time-dependent DFT, we calculate electronic and optical properties of a p-type/n-type polymeric blend, where we have chosen the poly(3,4-ethylenedioxythiophene)/benzimidazo-benzophenanthroline ladder (PEDOT/BBL) as a model composite system. We demonstrate that in the blend, PEDOT acts as an electron donor and BBL acts as an electron acceptor under doped conditions. However, no charge transfer between the chains takes place for an undoped composite system. Due to a significant difference in the electron affinities and the ionization energies of PEDOT and BBL, the electronic properties of a negatively (positively) doped PEDOT/BBL blend are primarily governed by the chains where negative (positive) charges are localized, i.e., the BBL chains (the PEDOT chains). However, this is no longer valid for the optical absorption where the electronic transition occurs between the two chains and, therefore, the calculated UV–vis–near-infrared (NIR) absorption spectra of the negatively (positively) doped PEDOT/BBL blend are rather different compared to the corresponding spectra of the single BBL chains (PEDOT chains). The electronic coupling between the photoexcited state and the final charge-transfer state of the blend was calculated to be ∼0.08 eV. The results presented here are generic to a wide class of p-type/n-type combinations, which was further confirmed by calculations performed on the polythiophene (PT)/BBL blendItem Experimental and Theoretical Investigation into the Polaron Structure of K-Doped Polyfluorene Films(ACS, 2020-12) Ghosh, SarbaniThe evolution of the electronic structure and optical transition upon n-doping of poly(9,9-dioctylfluorene) (PFO) films is elucidated with photoelectron spectroscopy, optical absorption, density functional theory (DFT), and time-dependent DFT (TD-DFT) calculations. Optical absorption measurements extending into near infrared show two low-energy absorption features at low doping ratios and an additional peak at a higher energy of ∼2.2 eV that disappears with increasing doping ratios. A gap state (i.e., polaronic state) close to the Fermi level and a significantly destabilized highest valence band appear in the experimentally measured ultraviolet photoelectron spectra. These experimental results are interpreted by the TD-DFT calculations, which show that the lower energy peaks originate from the excitation from polaronic states to the conduction band, while the higher energy peak mainly originates from the destabilized valence band to conduction band transitions and only appears at low doping ratios (cred ≤ 50%, 0.5 potassium atom per fluorene monomer). The DFT calculations further indicate that polaron pairs rather than bipolarons are preferentially formed at high doping ratios. Comparing the results of doped glassy and β-phase films, we find that the ordered segments in the β-phase film disappear due to the dopant (potassium) insertion, resulting in a similar polaronic structure.