Classical molecular dynamics (MD) simulations and quantum chemical density functional theory (DFT) calculations have been employed in the present study to investigate the solvation of lithium cations in pure organic carbonate solvents (ethylene carbo
nate (EC), propylene carbonate (PC) and dimethyl carbonate (DMC)) and their binary (EC-DMC, 1:1 molar composition) and ternary (EC-DMC-PC, 1:1:3 molar composition) mixtures. The results obtained by both methods indicate that the formation of complexes with four solvent molecules around Li+, exhibiting a strong local tetrahedral order, is the most favorable. However, the molecular dynamics simulations have revealed the existence of significant structural heterogeneities, extending up to a length scale which is more than five times the size of the first coordination shell radius. Due to these significant structural fluctuations in the bulk liquid phases, the use of larger size clusters in DFT calculations has been suggested. Contrary to the findings of the DFT calculations on small isolated clusters, the MD simulations have predicted a preference of Li+ to interact with DMC molecules within its first solvation shell and not with the highly polar EC and PC ones, in the binary and ternary mixtures. This behavior has been attributed to the local tetrahedral packing of the solvent molecules in the first solvation shell of Li+, which causes a cancellation of the individual molecular dipole vectors, and this effect seems to be more important in the cases where molecules of the same type are present. Due to these cancellation effects, the total dipole in the first solvation shell of Li+ increases when the local mole fraction of DMC is high.
Morphology of polymer electrolytes membranes (PEM), e.g., Nafion, inside PEM fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be fou
nd as an ultra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films has not been sufficiently explored yet. Here, we report about Molecular Dynamics simulation investigation of the substrate effects on the ionomer ultra-thin film morphology at different hydration levels. We use a mean-field-like model we introduced in previous publications for the interaction of the hydrated Nafion ionomer with a substrate, characterized by a tunable degree of hydrophilicity. We show that the affinity of the substrate with water plays a crucial role in the molecular rearrangement of the ionomer film, resulting in completely different morphologies. Detailed structural description in different regions of the film shows evidences of strongly heterogeneous behavior. A qualitative discussion of the implications of our observations on the PEMFC catalyst layer performance is finally proposed.
Structure of polymer electrolytes membranes, e.g., Nafion, inside fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be found as an ul
tra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films and, in turn, on transport properties, has not been sufficiently explored yet. Here, we report about classical Molecular Dynamics simulations of hydrated Nafion thin-films in contact with unstructured supports, characterized by their global wetting properties only. We have investigated structure and transport in different regions of the film and found evidences of strongly heterogeneous behavior. We speculate about the implications of our work on experimental and technological activity.
We follow the dynamics of an ensemble of interacting self-propelled motorized particles in contact with an equilibrated thermal bath. We find that the fluctuation-dissipation relation allows for the definition of an effective temperature that is comp
atible with the results obtained using a tracer particle as a thermometer. The effective temperature takes a value which is higher than the temperature of the bath and it is continuously controlled by the motor intensity.
We follow the dynamics of an ensemble of interacting self-propelled semi-flexible polymers in contact with a thermal bath. We characterize structure and dynamics of the passive system and as a function of the motor activity. We find that the fluctuat
ion-dissipation relation allows for the definition of an effective temperature that is compatible with the results obtained by using a tracer particle as a thermometer. The effective temperature takes a higher value than the temperature of the bath when the effect of the motors is not correlated with the structural rearrangements they induce. Our data are compatible with a dependence upon the square of the motor strength (normalized by the average internal force) and they suggest an intriguing linear dependence on the tracer diffusion constant times the density of the embedding matrix. We show how to use this concept to rationalize experimental results and suggest possible innovative research directions.
We use molecular dynamics simulations to study the dynamics of an ensemble of interacting self-propelled semi-flexible polymers in contact with a thermal bath. Our intention is to model complex systems of biological interest. We find that an effectiv
e temperature allows one to rationalize the out of equilibrium dynamics of the system. This parameter is measured in several independent ways -- from fluctuation-dissipation relations and by using tracer particles -- and they all yield equivalent results. The effective temperature takes a higher value than the temperature of the bath when the effect of the motors is not correlated with the structural rearrangements they induce. We show how to use this concept to interpret experimental results and suggest possible innovative research directions.
The low-temperature thermal properties of dielectric crystals are governed by acoustic excitations with large wavelengths that are well described by plane waves. This is the Debye model, which rests on the assumption that the medium is an elastic con
tinuum, holds true for acoustic wavelengths large on the microscopic scale fixed by the interatomic spacing, and gradually breaks down on approaching it. Glasses are characterized as well by universal low-temperature thermal properties, that are however anomalous with respect to those of the corresponding crystalline phases. Related universal anomalies also appear in the low-frequency vibrational density of states and, despite of a longstanding debate, still remain poorly understood. Using molecular dynamics simulations of a model monatomic glass of extremely large size, we show that in glasses the structural disorder undermines the Debye model in a subtle way: the elastic continuum approximation for the acoustic excitations breaks down abruptly on the mesoscopic, medium-range-order length-scale of about ten interatomic spacings, where it still works well for the corresponding crystalline systems. On this scale, the sound velocity shows a marked reduction with respect to the macroscopic value. This turns out to be closely related to the universal excess over the Debye model prediction found in glasses at frequencies of ~1 THz in the vibrational density of states or at temperatures of ~10 K in the specific heat.
