RESUMEN
The prediction of new organic photovoltaic materials in organic solar cells (OSCs) must include a precise description of charge-transfer states because they are involved in electron-transfer processes such as charge separation and charge recombination which govern the device efficiency. Also, as the experimental performance of an optoelectronic device is measured for nonequilibrium nanostructures, computational approaches need models that can incorporate morphology effects. Usually, this aspect is treated by molecular dynamics simulation (MDS) methodologies; however, methodologies and formalisms to calculate the electron-transfer processes are still controversial and sometimes do not connect their information with the phase morphologies. In this work we propose a simple and fast characterization of electron-transfer processes to find the rate constants by analysing the distribution of vertical excitation energies of both local excitation (LE) and charge-transfer (CT) states using TD-DFT calculations in the donor-acceptor pair structures which were extracted from MDS. This proposal assumes that conformational changes are prevented and equilibria are not achieved while the electron-transfer events take effect, and thus the only pathway that connects the LE and CT states is their surface crossing point where an ideal distribution might exist. Different density functionals and dialectric models were tested. The results indicate a close relationship between the proposal and experimental data for electron-transfer events, suggesting the application of this method in the rational design of new photovoltaic materials.
RESUMEN
Organic photovoltaic materials (OPVs), with low cost and structure flexibility, are of great interest and importance for their application in solar cell device development. However, the optimization of new OPV structures and the study of the structure arrangements and packing morphologies when materials are blended takes time and consumes raw materials, thus theoretical models could be of considerable value. In this work, we performed molecular dynamics simulations of present OPVs to understand the morphological packing of the donor-acceptor (DA) phases and DA heterojunction during evaporation and annealing processes, following inter and intramolecular properties like frontier orbitals, π-π stacking, coordination, distances, angles, and aggregation. Our considered donor molecules were selected from already proved experimental studies and also from predicted optimal compounds, designed through high throughput studies. The acceptor molecule employed in all our studied systems was PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). Furthermore, we also analyze the influence of including different lateral aliphatic chains on the structural properties of the resulting DA packing morphologies. Our results can guide the design of new OPVs and subsequent studies applying charge transport and charge separation models.
RESUMEN
Compounds from the 2,2'-bipyridine molecular family were investigated for use as redox-active materials in organic flow batteries. For 156 2,2'-bipyridine derivatives reported in the academic literature, we calculated the redox potential, the pKa for the second deprotonation reaction, and the solubility in aqueous solutions. Using experimental data on a small subset of derivatives, we were able to calibrate our calculations. We find that functionalization with electron-withdrawing groups leads to an increase of the redox potential and to an increase of the molecular acidity (as expressed in a reduction of the pKa value for the second deprotonation step). Furthermore, calculations of solubility in water indicate that some of the studied derivatives have adequate solubility for flow battery applications. Based on an analysis of the phyisco-chemical properties of the 156 studied compounds, we down-select five molecules with carbonyl- and nitro-based functional groups, whose parameters are especially promising for potential applications as negative redox-active materials in organic flow batteries.
RESUMEN
To investigate the relationship between atomic topology, vibrational and electronic properties and superconductivity of bismuth, a 216-atom amorphous structure (a-Bi216) was computer-generated using our undermelt-quench approach. Its pair distribution function compares well with experiment. The calculated electronic and vibrational densities of states (eDOS and vDOS, respectively) show that the amorphous eDOS is about 4 times the crystalline at the Fermi energy, whereas for the vDOS the energy range of the amorphous is roughly the same as the crystalline but the shapes are quite different. A simple BCS estimate of the possible crystalline superconducting transition temperature gives an upper limit of 1.3 mK. The e-ph coupling is more preponderant in a-Bi than in crystalline bismuth (x-Bi) as indicated by the λ obtained via McMillan's formula, λc = 0.24 and experiment λa = 2.46. Therefore with respect to x-Bi, superconductivity in a-Bi is enhanced by the higher values of λ and of eDOS at the Fermi energy.
