Electronic structure and optical absorption spectra of poly­(3,4-ethylenedioxythiophene) (PEDOT) for different oxidation levels were studied using density functional theory (DFT) and time-dependent DFT. It is shown, that the DFT-based predictions for the polaronic and bipolaronic states and the nature of corresponding optical transitions are qualitatively different from the widely used traditional picture based on semi-empirical pre-DFT approaches that still dominate the current literature. On the basis of the results of our calculations, the experimental Vis/NIR absorbance spectroscopy and the electron paramagnetic resonance spectroscopy are re-examined, and a new interpretation of the measured spectra and the spin signal, which is qualitatively different from the traditional interpretation, is provided. The findings and conclusions concerning the nature of polaronic and bipolaronic states, band structure and absorption spectra presented for PEDOT, are generic for a wide class of conducting polymers (such as polythiophenes and their derivatives) that have a similar structure of monomer units.

SignificancePlants with integrated electronics, e-Plants, have been presented recently. Up to now the devices and circuits have been manufactured in localized regions of the plant due to limited distribution of the organic electronic material. Here we demonstrate the synthesis and application of a conjugated oligomer that can be delivered in every part of the vascular tissue of a plant and cross through the veins into the apoplast of leaves. The oligomer polymerizes in vivo due to the physicochemical environment of the plant. We demonstrate long-range conducting wires and supercapacitors along the stem. Our findings open pathways for autonomous energy systems, distributed electronics, and new e-Plant device concepts manufactured in living plants.

Norbornadiene-quadricyclane (NBD-QC) photoswitches are candidates for applications in solar thermal energy storage. Functionally, they rely on an intramolecular [2+2] cycloaddition reaction, which couples the S landscape on the NBD side to the S landscape on the QC side of the reaction and vice-versa. This commonly results in an unfavourable correlation between the first absorption maximum and the barrier for thermal back-conversion. This work demonstrates that this correlation can be counteracted by using steric repulsion to hamper the rotational motion of the side groups along the back-conversion path. It is shown that this modification reduces the correlation between the effective back-conversion barrier and the first absorption maximum and also increases the back-conversion entropy. The resulting molecules exhibit exceptionally long half-lives for their metastable forms without significantly affecting other properties, most notably solar spectrum match and storage density.

Strong EM wave absorption and lightweight are the foremost important factors that drive the real-world applications of the modern microwave absorbers. This work mainly deals with the design of highly efficient microwave absorbers, where a hierarchical carbon nanotube (CNT) forest is first grown on the carbon fiber (CF) through the catalytic chemical vapor deposition method. The hierarchical carbon nanotube grown on the carbon fiber (CNTCF) is then embedded in the epoxy matrix to synthesize lightweight nanocomposites for their use as efficient microwave absorbers. The morphological study shows that carbon nanotubes (CNTs) self-assemble to form a trapping center on the carbon fiber. The electromagnetic characteristics of resultant nanocomposites are investigated exclusively in the X-band (8.2-12.4 GHz) using the network analyzer. The synthesized nanocomposites, containing 0.35 and 0.50 wt % CNTCFs, exhibit excellent microwave absorption properties, which could be attributed to the better impedance matching conditions and high dielectric losses. The reflection loss (RL) of -42.0 dB (99.99% absorption) with -10 dB (90% absorption) and -20 dB (99% absorption) bandwidths of 2.7 and 1.16 GHz, respectively, is achieved for 0.35 wt % CNTCF loading at 2.5 mm thickness. The composite with 0.50 wt % CNTCF loading illustrates substantial absorption efficiency with the RL reaching -24.5 dB (99.65% absorption) at 9.8 GHz and -10 dB bandwidth comprising 84.5% of the entire X band. The excellent microwave properties obtained here are primarily due to the electric dipole polarization, interfacial polarization, and unique trapping center. These trapping centers basically induce multiple reflections and scatterings, which attenuate more microwave energy. This investigation opens a new approach for the development of extremely lightweight, small-thickness, and highly efficient microwave absorbers for X-band applications.

Doped material is an innovation in developing the lightweight microwave absorbing material. Herein, heteroatom-doped carbon is synthesized by pyrolysis of chicken feather fibers (CFFs) in the temperature range of 400−1400 °C. The synthesis method exhibits that poultry waste is more nature-friendly as no external hazardous dopants are used during pyrolysis, and it has a much lower cost. The morphology and structural characteristics have been studied via SEM, AFM, TEM, XRD, Raman, and XPS. The density of surface chemical states, defects, roughness, and structural property are found to vary significantly with pyrolysis temperature. The electromagnetic properties of CFF/epoxy composites have been studied in the frequency range of 8.2−12.4 GHz (X band). In addition, the correlations between pyrolysis temperature and absorption properties are established. High absorption properties at temperature ≥800 °C are attributed to the large fraction of heteroatoms, defects, surface roughness, and high porosity. In addition, the CFF pyrolyzed at 1400 °C is further activated with potassium hydroxide that results in numerous porous morphologies with large surfaces. This optimized porous CFF illustrates substantial absorption efficiency corresponding to the absorber thickness of 1.68 mm and RL of −44.6 dB (99.99% microwave absorption), which exhibits a broad −10 dB (90% absorption) bandwidth that shares 52.9% of the entire X band frequency width. The strong microwave absorption originates from defect polarization, electric/dipolar polarization, interfacial polarization, and 3D porous structure. The porous 3D architecture improves the impedance matching and can generate multiple reflections and scattering of electromagnetic waves, which attenuate microwave waves largely. This work suggests that the heteroatom-doped carbon derived from CFF is a potential candidate to design a lightweight and efficient microwave absorber.

Large scale atomistic simulations using the reactive force field approach (ReaxFF) are implemented to investigate the thermomechanical properties of fluorinated graphene (FG). A new set of parameters for the reactive force field potential (ReaxFF) optimized to reproduce key quantum mechanical properties of relevant carbon-fluor cluster systems are presented. Molecular dynamics (MD) simulations are used to investigate the thermal rippling behavior of FG and its mechanical properties and compare them with graphene (GE), graphane (GA) and a sheet of BN. The mean square value of the height fluctuations h 2 and the height-height correlation function H(q) for different system sizes and temperatures show that FG is an un-rippled system in contrast to the thermal rippling behavior of graphene (GE). The effective Young's modulus of a flake of fluorinated graphene is obtained to be 273 N/m and 250 N/m for a flake of FG under uniaxial strain along arm-chair and zig-zag direction, respectively.

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 97–104

The structural, electronic and magnetic properties of single layers of Iron Dichloride (FeCl2) were calculated using first principles calculations. We found that the 1T phase of the single layer FeCl2 is 0.17 eV/unit cell more favorable than its 1H phase. The structural stability is confirmed by phonon calculations. We found that 1T-FeCl2 possess three Raman-active (130, 179 and 237 cm −1 ) and one Infrared-active (279 cm −1 ) phonon branches. The electronic band dispersion of the 1T-FeCl2 is calculated using both GGA-PBE and DFT-HSE06 functionals. Both functionals reveal that the 1T-FeCl2 has a half-metallic ground state with a Curie temperature of 17 K.