Disorder-Induced Transition from Transient Quantum Delocalization to Charge Carrier Hopping Conduction in a Nonfullerene Acceptor Material

Nonfullerene acceptors have caused a step change in organic optoelectronics research but little is known about the mechanism and factors limiting charge transport in these molecular materials. Here a joint computational-experimental investigation is presented to understand the impact of various sources of disorder on the electron transport in the nonfullerene acceptor O-IDTBR. We find that in single crystals of this material, electron transport occurs in the transient quantum delocalization regime with the excess charge delocalized over about three molecules on average, according to quantum-classical nonadiabatic molecular-dynamics simulations. In this regime, carrier delocalization and charge mobility (μa 1⁄4 7 cm2 V−1 s−1) are limited by dynamical disorder of off-diagonal and diagonal electron-phonon coupling. In molecular assemblies representing disordered thin films, the additional static disorder of off- diagonal electron-phonon coupling is sufficient to fully localize the excess electron on single molecules, concomitant with a transition of transport mechanism from transient quantum delocalization to small polaron hopping and a drop in electron mobility by about 1 order of magnitude. Yet, inclusion of static diagonal disorder resulting from electrostatic interactions arising from the acceptor-donor-acceptor (A-D-A) structure of O-IDTBR, are found to have the most dramatic impact on carrier mobility, resulting in a further drop of electron mobility by about 4–5 orders of magnitude to 10−5 cm2 V−1 s−1, in good agreement with thin-film electron mobility estimated from space-charge-limited-current measurements. Limitations due to diagonal disorder caused by electrostatic interactions are likely to apply to most nonfullerene acceptors. They imply that while A-D-A or A-DAD-A motifs are beneficial for photo- absorption and exciton transport, the electrostatic disorder they create can limit carrier transport in thin-film optoelectronic applications. This work shows the value of computational methods, in particular, nonadiabatic molecular-dynamics propagation of charge carriers, to distinguish different regimes of transport for different types of molecular packing

Nonadiabatic Dynamics of Cycloparaphenylenes with TD-DFTB Surface Hopping

We implemented a version of the decoherence-corrected fewest switches surface hopping based on linear-response time-dependent density functional tight binding (TD-DFTB), enhanced by transition density analysis. The method has been tested for the gas-phase relaxation dynamics of two cycloparaphenylene molecules, [8]­CPP and [10]­CPP, explaining some important features of their nonadiabatic dynamics, such as the origin of their long fluorescence lifetimes (related to the slow radiative emission from the S₁ state) and the trend of increasing the fluorescence rate with the molecular size (related to an increase in the S₁–S₀ energy gaps and oscillator strengths in the larger molecule). The quality of the TD-DFTB electronic structure information was assessed through four quantities: excitation energies; charge-transfer (CT) numbers, which estimate the charge transfer character of states; participation ratio (PR), which describes delocalization of electronic density; and participation ratio of natural transition orbitals (PRNTO), which describes the multiconfigurational character of states. These quantities were computed during dynamics and recomputed for the same geometries with the higher-level long-range-corrected TD-LC-DFTB and a lower-level single-determinant approximation for the excited states, SD-(LC)-DFTB. Taking TD-LC-DFTB as the standard, TD-DFTB underestimates the excitation energies by ∼0.5 eV and overestimates CT and PR. SD-DFTB underestimates excitation energies and overestimates CT to the same extent that TD-DFTB does, but it predicts reasonable PR distributions. SD-LC-DFTB leads to an extreme overestimation of the excitation energies by ∼3 eV, overestimates the charge transfer character of the state, but predicts the PR values very close to those obtained with TD-LC-DFTB

Simultaneous Removal of Divalent Heavy Metals from Aqueous Solutions Using Raw and Mechanochemically Treated Interstratified Montmorillonite/Kaolinite Clay

The removal of Pb­(II), Cd­(II), Cu­(II), and Zn­(II) from aqueous solutions using (un)­modified Serbian interstratified montmorillonite/kaolinite clay as an adsorbent was investigated. The clay was modified by mechanochemical activation for different time periods. X-ray diffraction patterns and particle size distributions were used to characterize the samples. Batch adsorption studies were conducted to optimize various conditions. The adsorption equilibrium was established within 60 min, and the maximum adsorption occurred in the pH range of 4.5–6.5. The milled clays exhibited greater equilibrium adsorption capacities (<i>q</i>_e) for all of the metals than the raw clay. A difference in <i>q</i>_e values for clays milled for 2 and 19 h could be observed only for initial concentrations (<i>C</i>_i) of ≥100 mg dm^–3. This was related to the amorphization (i.e., exfoliation) of 19-h-milled clay particles. The adsorption equilibrium data of heavy metals on both raw and modified clays fit the Langmuir equation, although there were changes in the microstructure of the clay. The mechanochemical treatment of the clay reduced the amount of adsorbent necessary to achieve a highly efficient removal of heavy metals by a factor of 5. Thus, the mechanochemically treated interstratified clay can be considered as an efficient adsorbent for the simultaneous removal of divalent heavy metals