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Polyelectrolyte materials are an interesting class of electrolytes for use in fuel cell and battery applications. Poly(para-phenylene terephthalamide) (PPTA, Kevlar) is a liquid crystalline polymer that, when sulfonated, is a polyelectrolyte that exhibits moderate ion conductivity at elevated temperatures. In this work, quasi-elastic neutron scattering (QENS) experiments were performed to gain insight into the effect of the presence of lithium counterions on the chain dynamics in the material. It was found that the addition of lithium ions decreases the dynamics of the chains. Additionally, the binding of lithium ions to the sulfonic acids groups was investigated by density functional theory (DFT) calculations. It was found that the local surroundings of the sulfonic acid group have very little effect on the lithium-ion binding energy. Binding energies for a variety of different systems were all calculated to be around 150 kcal/mol. The DFT calculations also show the existence of a structure in which a single lithium ion interacts with two sulfonic acid moieties on different chains. The formation of such "electrostatic cross-links" is believed to be the source of the increased tendency to aggregate and the reduced dynamics in the presence of lithium ions.

The electronic structure and optical properties of charged oligofluorenes were studied experimentally and theoretically. Measurements of the optical absorption spectra of charged oligofluorenes in dilute solutions have been performed by using the pulse radiolysis technique. In addition, optical absorption spectra of radical cations and anions in a solid matrix were measured after gamma-irradiation at 77 K. The optical absorption spectra were measured in the range of 440-2100 nm (0.6-2.8 eV) and compared with results from time-dependent density functional theory (TDDFT) calculations. The calculated charge induced deformations and charge distribution do not indicate the occurrence of polaronic effects. The potential energy profiles for rotation around the inter-unit bond show that oligofluorenes are nonplanar in their neutral state, while they tend to more planar structures in their charged state. The optical absorption spectra of charged oligofluorenes are dependent on the angle between neighboring units. TDDFT absorption energies shift to lower values with increasing chain length, which suggests that the charge delocalizes along the oligomer chain.

We have studied the real and imaginary parts of the complex intrachain mobility of charge carriers on solid samples of ladder-type polymers using time-resolved microwave conductivity measurements. Experiments on samples with a different average polymer chain length show that the motion of charge carriers is limited by the chain ends. The experimental results can be described by one-dimensional diffusive motion along the polymer backbone. The intrachain mobility deduced for an infinitely long ladder-type polymer chain (with no barriers to charge transport such as defects or conjugation breaks) subject to interchain interactions is $30\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{2}∕\mathrm{V}\phantom{\rule{0.2em}{0ex}}\mathrm{s}$. This value is 20 times lower than the intrachain mobility found for charges along infinitely long isolated ladder-type polymer chains in dilute solution. Thus we find that interchain interactions in solid samples severely decrease the intrachain charge carrier mobility. However, the intrachain mobility of $30\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{2}∕\mathrm{V}\phantom{\rule{0.2em}{0ex}}\mathrm{s}$ is more than four orders of magnitude higher than mobility values obtained from time of flight measurements reported in the literature. Hence, the performance of ladder-type polymers in optoelectronic devices can be significantly improved.

In this paper the role of the solvent in the formation of the charge-separated excited state of 9,9'-bianthryl (BA) is examined by means of mixed molecular mechanical/quantum mechanical (QM/MM) calculations. It is shown that in weakly polar solvents a relaxed excited state is formed with an interunit angle that is significantly smaller than 90 degrees. This relaxed excited state has a considerable dipole moment even in weakly polar solvents; for benzene and dioxane dipole moments of ca. 6 D were calculated, which is close to experimental data. These dipoles are induced by the solvent in the highly polarizable relaxed excited state of BA, and the dipole relaxation time is governed by solvent reorganizations. In polar solvent the charge separation is driven to completion by the stronger dipoles in the solvent and a fully charged separated excited state is formed with an interunit angle of 90 degrees.

The optoelectronic properties of dilute solutions of oligomeric and (broken-conjugation) polymeric phenylenevinylene chains were studied using the following techniques: optical absorption and (time-resolved) emission spectrophotometry, flash-photolysis time-resolved (real and imaginary) microwave conductivity, pulse-radiolysis time-resolved microwave conductivity, and pulse-radiolysis time-resolved optical absorption spectrophotometry. The following properties were determined: absorption and emission spectra, fluorescence quantum yields and decay times, exciton polarizabilities and dissociation probabilities, charge mobilities, and radical cation absorption spectra. The experimental results are compared with theoretical calculations of exciton polarizabilities, charge mobilities, and radical cation absorption spectra.

The effective energy of a positive charge when it is localized at a specific guanine nucleobase in DNA was calculated using density functional theory. The results demonstrate that the efficiency of a guanine to act as a hole-trap in DNA strongly depends on the nature of the flanking nucleobases. The presence of a pyrimidine base at the 3′ position adjacent to a guanine significantly increases the localization energy of the positive charge. The calculated distributions of a positive charge in sequences of two or three adjacent guanines, flanked by other nucleobases, provide an explanation for experimental literature data on the site-selective oxidation of DNA. Copyright © 2003 American Chemical Society.

Polyfluorenes (PFs) are conjugated polymers with exciting optical and electronic properties and potential applications in optoelectronics. Due to the liquid-crystalline character of most polyfluorene homopolymers, thin layers with a large degree of in-plane alignment can be fabricated with these polymers. Upon appropriate substitution of the polyfluorene backbone, layers with an optical anisotropy in absorption and polarization ratios in emission of more than twenty have recently been fabricated. When included in an organic light-emitting diode structure, highly-polarized blue electroluminescence with an integrated polarization ratio of up to 22 at a brightness of 800 cd/A was realized. These devices represent potential candidates for the illumination of LC displays. Investigations on the anisotropy of the charge carrier mobility revealed that the mobility is highly anisotropic, with only a very small mobility perpendicular to the polymer chains. This is in agreement with expectations based on the results of electron-microscopy studies, which established a structure in which the charge-conducting PF backbone is surrounded by a coaxial, insulating mantle of hydrocarbon side chains. Polyfluorene chains can thus be considered as semiconducting wires, which contain the insulation within their chemical structure.

A consistent derivation is given for local field factors to be used for correcting measured or calculated static (hyper)polarizabilities in the condensed phases. We show how local fields should be used in the coupled perturbative Hartree–Fock or finite field methods for calculating these properties, specifically for the direct reaction field (DRF) approach, in which a quantum chemically treated “solute” is embedded in a classical “solvent” mainly containing discrete molecules. The derivation of the local fields is based on a strictly linear response of the classical parts and they are independent of any quantum mechanical method to be used. In applications to two water dimers in two basis sets it is shown that DRF matches fully quantum mechanical results quite well. For acetone in eleven different solvents we find that if the solvent is modeled by only a dielectric continuum (hyper)polarizabilities increase with respect to their vacuum values, while with the discrete model they decrease. We show that the use of the Lorentz field factor for extracting (hyper)polarizabilities from experimental susceptibilities may lead to serious errors.

The Direct Reaction Field approach is briefly reviewed. Preliminary reports of the calculations on solvent induced shifts in the p * ˆ n transition of acetone in various solvents, and the dissociation of tert-butyl chloride in water are given. q 1999 Elsevier Science B.V. All rights reserved.

Discotic mesophases are known for their ability to self-assemble into columnar structures which serve as semiconducting molecular wires. Charge-carrier mobility along these wires strongly depends on molecular packing which is controlled by intermolecular interactions. Using solid-state NMR and molecular dynamics simulations we relate how conformations of alkyl and glycol side chains affect helical pitch and angular distribution of molecules within the columnar structures of perylenediimide derivatives. Using the high-temperature limit of Marcus theory we then establish a link between the secondary structure and charge-carrier mobility. Simulation results are compared to pulse-radiolysis time-resolved microwave conductivity measurements. We conclude that for achieving high charge-carrier mobilities in discotics, side chains with specific interactions are required in order to minimize the translational and orientational molecular disorder in the columns.

The charge carrier mobility in bulk samples of α,ω-dihexylquaterthiophene has been determined as a function of temperature using the Pulse-Radiolysis Time-Resolved-Microwave-Conductivity and Thin Film Transistor (TFT) techniques. The mobility values obtained at room temperature were 0.01 cm 2 /Vs for both methods However upon cooling to 150 K the FET mobility decreases by an order of magnitude whereas the TRMC mobility remains almost constant. This behaviour is interpreted as an effect of the frequency of the electric field that is used in the experiments and could be described theoretically using an over-the-barrier hopping model for the mobility.

The charge carrier mobility in bulk samples of regioregular poly-3-hexylthiophene is determined from -100 to +140°C with the pulse-radiolysis time-resolved microwave conductivity technique. The lower limit to the mobility obtained increases only slightly with temperature in this range from 0.003 cm 2 /Vs to 0.01 cm 2 /Vs. However, the decay kinetics of the charge carriers is strongly dependent on temperature. This is attributed to changes in the effective domain size in which the charge carriers are able to move.

A series of 1,3,5-benzenetrisamide derivatives with three hexaalkoxytriphenylene pendant groups were prepared, in which the triphenylene groups are connected to the central 1,3,5-benzenetrisamide core through a flexible spacer. The length of this spacer, as well as the size of the ortho-substituent at the triphenylene core, influences the columnar packing of these molecules. All compounds show liquid crystalline behavior with high isotropization temperatures. Different columnar hexagonal phases (Colh, Colhp, Colobl and Colr) have been identified using optical polarization microscopy, differential scanning calorimetry and X-ray diffraction. A chiral 1,3,5-benzenetrisamide derivative forms columnar stacks with a single helical sense, both in an apolar solvent and in a film, as observed by circular dichroism studies. Pulse radiolysis time-resolved microwave conductivity (PR-TRMC) studies show that the high ordering in a Colhp phase results in high charge carrier mobilities. On the other hand, the highest mobility was observed for the chiral compound, which has a Colr ordering.

We describe and characterize a microwave transmission setup for the measurement of radiation-induced transient conductivities in the frequency range between 26 and 38GHz (Q band). This technique combines the virtues of two already existing techniques. On one hand, the microwave transmission technique is well established for the determination of (quasi)static conductivities, but requires adaptations to be suitable to the determination of transient conductivities with 1ns temporal resolution. On the other hand, the transient conductivity technique is well established, too, but in its present form (using a reflection configuration) it suffers from a poor signal to noise ratio due to unwanted interferences. These interferences are due to the circulator, which diverts part of the incoming microwave flux directly to the detector. We characterized the transmission setup by measuring the real and imaginary components of the conductivity of pulse irradiated CO2 gas at different pressures, and compared these result...

The optoelectronic properties of hybrid perovskites can be easily tailored by varying their components. Specifically, mixing the common short organic cation (methylammonium (MA)) with a larger one (e.g., butyl ammonium (BA)) results in 2-dimensional perovskites with varying thicknesses of inorganic layers separated by the large organic cation. In both of these applications, a detailed understanding of the dissociation and recombination of electron-hole pairs is of prime importance. In this work, we give a clear experimental demonstration of the interconversion between bound excitons and free charges as a function of temperature by combining microwave conductivity techniques with photoluminescence measurements. We demonstrate that the exciton binding energy varies strongly (between 80 and 370 meV) with the thickness of the inorganic layers. Additionally, we show that the mobility of charges increases with the layer thickness, in agreement with calculated effective masses from electronic structure calculations.

We present ab initio calculations (DFT and SOC-G0W0) of the optoelectronic properties of different hybrid-halide perovskites, namely X-PbI3 (X = methylamonimum, formamidinium, guanidinium, hydrazinium, and hydroxylammonium). These calculations shed new light on how the substitution of different organic cations in the material influences its optoelectronic properties. Our simulations show a significant modification of the lattice parameter and band gap of the material upon cation substitution. These modifications are not only due to steric effects but also due to electrostatic interactions between the organic and inorganic parts of the material. In addition to this, we demonstrate how the relative orientations of neighboring cations in the material modify the local electrostatic potential of the system and its fundamental band gap. This change in the band gap is accompanied by the formation of localized and spatially separated electronic states. These localized states modify the carrier mobility in the materials and can be a reason for the formation and recombination of the charge carriers in these very promising materials.

Two-dimensional (2D) halide perovskites are a class of materials in which 2D layers of perovskite are separated by large organic cations. Conventionally, the 2D perovskites incorporate organic cations as spacers, but these organic cations also offer a route to introduce specific functionality in the material. In this work, we demonstrate, by density functional theory calculations, that the introduction of electron withdrawing and electron donating molecules leads to the formation of localized states, either in the organic or the inorganic part. Furthermore, we show that the energy of the bands located in the organic and inorganic parts can be tuned independently. The organic cation levels can be tuned by changing the electron withdrawing/donating character, whereas the energy levels in the inorganic part can be modified by varying the number of inorganic perovskite layers. This opens a new window for the design of 2D perovskites with properties tuned for specific applications.

Recently, halide double perovskites (HDPs), such as Cs2AgBiBr6, have been reported as promising nontoxic alternatives to lead halide perovskites. However, it remains unclear whether the charge-transport properties of these materials are as favorable as for lead-based perovskites. In this work, we study the mobilities of charges in Cs2AgBiBr6 and in mixed antimony-bismuth Cs2AgBi1-xSbxBr6, in which the band gap is tunable from 2.0 to 1.6 eV. Using temperature-dependent time-resolved microwave conductivity techniques, we find that the mobility is proportional to T-p (with p ≈ 1.5). Importantly, this indicates that phonon scattering is the dominant scattering mechanism determining the charge carrier mobility in these HDPs similar to the state-of-the-art lead-based perovskites. Finally, we show that wet chemical processing of Cs2AgBi1-xSbxBr6 powders is a successful route to prepare thin films of these materials, which paves the way toward photovoltaic devices based on nontoxic HDPs with tunable band gaps.

The excited-state dynamics of perylene-based bichromophoric light harvesting antenna systems has been tailored by systematic modification of the molecular structure and by using solvents of increasing polarity in the series toluene, chloroform, and benzonitrile. The antenna systems consist of blue light absorbing naphthalene monoimide (NMI) energy donors (D1, D2, and D3) and the perylene derived green light absorbing energy acceptor moieties, 1,7-perylene-3,4,9,10-tetracarboxylic tetrabutylester (A1), 1,7-perylene-3,4,9,10-tetracarboxylic monoimide dibutylester (A2), and 1,7-perylene-3,4,9,10-tetracarboxylic bisimide (A3). The design of these antenna systems is such that all exhibit ultrafast excitation energy transfer (EET) from the excited donor to the acceptor, due to the effective matching of optical properties of the constituent chromophores. At the same time, electron transfer from the donor to the excited acceptor unit has been limited by the use of a rigid and nonconjugated phenoxy bridge to link the donor and acceptor components. The antenna molecules D1A1, D1A2, and D1A3, which bear the least electron-rich energy donor, isopentylthio-substituted NMI D1, exhibited ultrafast EET (ωEET ∼ 1 ps) but no charge transfer and, resultantly, emitted a strong yellow-orange acceptor fluorescence upon excitation of the donor. The other antenna molecules D2A2, D2A3, and D3A3, which bear electron-rich energy donors, the amino-substituted NMIs D2 and D3, exhibited ultrafast energy transfer that was followed by a slower (ca. 20-2000 ps) electron transfer from the donor to the excited acceptor. This charge transfer quenched the acceptor fluorescence to an extent determined by molecular structure and solvent polarity. These antenna systems mimic the primary events occurring in the natural photosynthesis, i.e., energy capture, efficient energy funneling toward the central chromophore, and finally charge separation, and are suitable building blocks for achieving artificial photosynthesis, because of their robustness and favorable and tunable photophysical properties.

Low-dimensional lead halide hybrid perovskites are nowadays in the spotlight because of their improved stability and extensive chemical flexibility compared to their 3D perovskite counterparts, the current challenge being to design functionalized organic cations. Here, we report on the synthesis and full characterization of a perovskite-like hybrid (a perovskitoid) where the 1D lead iodide layout is patterned with a donor−acceptor charge transfer complex (CTC) between pyrene and tetracyanoquinodimethane, with a chemical formula of (C20H17NH3)PbI3·(C12H4N4). By combining multiple structural analysis and spectroscopic techniques with ab initio modeling, we show that the electronic, optical, and charge-transport properties of the hybrid materials are dominated by the organic CTC, with the inorganic backbone primarily acting as a template for the organization of the donor and acceptor molecules. Interestingly, time-resolved microwave conductivity (TRMC) measurements show an enhanced photocurrent generation in the 1D hybrid compared to the pure organic charge-transfer salt, likely associated with transient localization of the holes on the lead-iodide octahedra. This observation is in line with the close energy resonance between the valence crystal orbitals of the lead-iodide lattice and the frontier occupied molecular orbitals of pyrene predicted by the DFT calculations. Therefore, it paves the way toward the design of new hybrid low-dimensionality perovskites offering a synergic combination of organic and inorganic functionalities. The FWO is acknowledged for the funding of research. W.V.G. is an SB Ph.D. fellow at FWO (Number 1S17516N), R.H. is a special research fund (BOF) doctoral (Ph.D.) student at UHasselt/IMO. K.V.H. thanks the Hercules Foundation (Project AUGE/11/029 "3D -SPACE: 3D Structural Platform Aiming for Chemical Excellence") and the special research fund (BOF) Ugent (Project 01N03217) for funding. The work has been carried out in the context of the solliance network (www.solliance.eu), of which UHasselt and TUDe1ft are members. Additionally UHasselt is a 'partner in the Energyville Consortium (http://www.energyville.be/aboutenergyville).The research leading to these results in the Delft University of Technology has received funding from the European Research Council Horizon 2020 ERC Grant Agreement No. 648433. The work from the University of Mons was supported by a 50-50 Ph.D. funding for N.M. from the University of Mons, by the Interuniversity Attraction Pole program of the Belgian Referal Science Policy Office (PAI 6/27) and FNRS-F.R.S. Computational resources have been provided by the Consortium des Equipements de Calcul Intensif (CECI), funded by the Fonds de la Recherche Scientifique de Belgique (F.RS.-FNRS) under Grant No. 2.5020.1 and by the Walloon Region. C.Q and D.B. are a FNRS postdoctoral researcher and research director, respectively. Bart Ruttens and Jan D'Haen (IMO-IMOMEC) are acknowledged for PXRD measurements.

Double perovskites, comprising two different cations, are potential nontoxic alternatives to lead halide perovskites. Here, we characterized thin films and crystals of Cs2AgBiBr6 by time-resolved microwave conductance (TRMC), which probes formation and decay of mobile charges upon pulsed irradiation. Optical excitation of films results in the formation of charges with a yield times mobility product, φΣμ > 1 cm2/Vs. On excitation of millimeter-sized crystals, the TRMC signals show, apart from a fast decay, a long-lived tail. Interestingly, this tail is dominant when exciting close to the bandgap, implying the presence of mobile charges with microsecond lifetimes. From the temperature and intensity dependence of the TRMC signals, we deduce a shallow trap state density of around 1016/cm3 in the bulk of the crystal. Despite this high concentration, trap-assisted recombination of charges in the bulk appears to be slow, which is promising for photovoltaic applications.

In this contribution we demonstrate a solid-state approach to triplet-triplet annihilation upconversion for application in a solar cell device in which absorption of near-infrared light is followed by direct electron injection into an inorganic substrate. We use time-resolved microwave photoconductivity experiments to study the injection of electrons into the electron-accepting substrate (TiO2) in a trilayer device consisting of a triplet sensitizer (fluorinated zinc phthalocyanine), triplet acceptor (methyl subsituted perylenediimide), and smooth polycrystalline TiO2. Absorption of light at 700 nm leads to the almost quantitative generation of triplet excited states by intersystem crossing. This is followed by Dexter energy transfer to the triplet acceptor layer where triplet annihilation occurs and concludes by injection of an electron into TiO2 from the upconverted singlet excited state.

Formamidinium (FA) lead iodide perovskite materials feature promising photovoltaic performances and superior thermal stabilities. However, conversion of the perovskite α-FAPbI3 phase to the thermodynamically stable yet photovoltaically inactive δ-FAPbI3 phase compromises the photovoltaic performance. A strategy is presented to address this challenge by using low-dimensional hybrid perovskite materials comprising guaninium (G) organic spacer layers that act as stabilizers of the three-dimensional α-FAPbI3 phase. The underlying mode of interaction at the atomic level is unraveled by means of solid-state nuclear magnetic resonance spectroscopy, X-ray crystallography, transmission electron microscopy, molecular dynamics simulations, and DFT calculations. Low-dimensional-phase-containing hybrid FAPbI3 perovskite solar cells are obtained with improved performance and enhanced long-term stability.

With femtosecond pump-probe spectroscopy we found for photocatalytically active NH2-MIL-125 that after photo-excitation the hole resides on -NH2. Charge transfer from the MOF to an occluded molecule capable to shuttle single charges to a reaction centre is extremely fast (< 200 fs) while charge recombination only occurs on the ns-μs time scale.