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Creators/Authors contains: "de Pablo, Juan J."

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  1. Free, publicly-accessible full text available May 23, 2024
  2. Free, publicly-accessible full text available April 26, 2024
  3. Fluoroether solvents are promising electrolyte candidates for high-energy-density lithium metal batteries, where high ionic conductivity and oxidative stability are important metrics for design of new systems. Recent experiments have shown that these performance metrics, particularly stability, can be tuned by changing the fraction of ether and fluorine content. However, little is known about how different molecular architectures influence the underlying ion transport mechanisms and conductivity. Here, we use all-atom molecular dynamics simulations to elucidate the ion transport and solvation characteristics of fluoroether chains of varying length, and having different ether segment and fluorine terminal group contents. The design rules that emerge from this effort are that solvent size determines lithium-ion transport kinetics, solvation structure, and solvation energy. In particular, the mechanism for lithium-ion transport is found to shift from ion hopping between solvation sites located in different fluoroether chains in short-chain solvents, to ion–solvent co-diffusion in long-chain solvents, indicating that an optimum exists for molecules of intermediate length, where hopping is possible but solvent diffusion is fast. Consistent with these findings, our experimental measurements reveal a non-monotonic behavior of the effects of solvent size on lithium-ion conductivity, with a maximum occurring for medium-length solvent chains. A key design principle for achieving high ionic conductivity is that a trade-off is required between relying on shorter fluoroether chains having high self-diffusivity, and relying on longer chains that increase the stability of local solvation shells. 
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  4. Free, publicly-accessible full text available June 1, 2024
  5. Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena. 
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  6. Active materials are those in which individual, uncoordinated local stresses drive the material out of equilibrium on a global scale. Examples of such assemblies can be seen across scales from schools of fish to the cellular cytoskeleton and underpin many important biological processes. Synthetic experiments that recapitulate the essential features of such active systems have been the object of study for decades as their simple rules allow us to elucidate the physical underpinnings of collective motion. One system of particular interest has been active nematic liquid crystals (LCs). Because of their well understood passive physics, LCs provide a rich platform to interrogate the effects of active stress. The flows and steady state structures that emerge in an active LCs have been understood to result from a competition between nematic elasticity and the local activity. However most investigations of such phenomena consider only the magnitude of the elastic resistance and not its peculiarities. Here we investigate a nematic liquid crystal and selectively change the ratio of the material's splay and bend elasticities. We show that increases in the nematic's bend elasticity specifically drives the material into an exotic steady state where elongated regions of acute bend distortion or “elasticity bands” dominate the structure and dynamics. We show that these bands strongly influence defect dynamics, including the rapid motion or “catapulting” along the disintegration of one of these bands thus converting bend distortion into defect transport. Thus, we report a novel dynamical state resultant from the competition between nematic elasticity and active stress. 
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  7. Autonomous experimental systems offer a compelling glimpse into a future where closed-loop, iterative cycles—performed by machines and guided by artificial intelligence (AI) and machine learning (ML)—play a foundational role in materials research and development. This perspective draws attention to the roles of networks and interfaces—of and between humans and machines—for the purpose of generating knowledge and accelerating innovation. Polymers, a class of materials with massive global impact, present a unique opportunity for the application of informatics and automation to pressing societal challenges. To develop these networks and interfaces in polymer science, the Community Resource for Innovation in Polymer Technology (CRIPT)—a polymer data ecosystem based on novel polymer data model, representation, search, and visualization technologies—is introduced. The ongoing co-design efforts engage stakeholders in industry, academia, and government to uncover rapidly actionable, high-impact opportunities to build networks, bridge interfaces, and catalyze innovation in polymer technology. 
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