Gerrick E. Lindberg

Hydroxide Solvation and Transport in Anion Exchange Membranes

Understanding hydroxide solvation and transport in anion exchange membranes (AEMs) can provide important insight into the design principles of these new membranes. To accurately model hydroxide solvation and transport, we developed a new multiscale reactive molecular dynamics model for hydroxide in aqueous solution, which was then subsequently modified for an AEM material. With this model, we investigated the hydroxide solvation structure and transport mechanism in the membrane. We found that a relatively even separation of the rigid side chains produces a continuous overlapping region for hydroxide transport that is made up of the first hydration shell of the tethered cationic groups. Our results show that hydroxide has a significant preference for this overlapping region, transporting through it and between the AEM side chains with substantial contributions from both vehicular (standard diffusion) and Grotthuss (proton hopping) mechanisms. Comparison of the AEM with common proton exchange membranes (PEMs) showed that the excess charge is less delocalized in the AEM than the PEMs, which is correlated with a higher free energy barrier for proton transfer reactions. The vehicular mechanism also contributes considerably more than the Grotthuss mechanism for hydroxide transport in the AEM, while our previous studies of PEM systems showed a larger contribution from the Grotthuss mechanism than the vehicular mechanism for proton transport. The activation energy barrier for hydroxide diffusion in the AEM is greater than that for proton diffusion in PEMs, implying a more significant enhancement of ion transport in the AEM at elevated temperatures.

Propensity of Hydrated Excess Protons and Hydroxide Anions for the Air–Water Interface

Significant effort has been undertaken to better understand the molecular details governing the propensity of ions for the air-water interface. Facilitated by computationally efficient reactive molecular dynamics simulations, new and statistically conclusive molecular-scale results on the affinity of the hydrated excess proton and hydroxide anion for the air-water interface are presented. These simulations capture the dynamic bond breaking and formation processes (charge defect delocalization) that are important for correctly describing the solvation and transport of these complex species. The excess proton is found to be attracted to the interface, which is correlated with a favorable enthalpic contribution and consistent with reducing the disruption in the hydrogen bond network caused by the ion complex. However, a recent refinement of the underlying reactive potential energy function for the hydrated excess proton shows the interfacial attraction to be weaker, albeit nonzero, a result that is consistent with the experimental surface tension measurements. The influence of a weak hydrogen bond donated from water to the protonated oxygen, recently found to play an important role in excess hydrated proton transport in bulk water, is seen to also be important for this study. In contrast, the hydroxide ion is found to be repelled from the air-water interface. This repulsion is characterized by a reduction of the energetically favorable ion-water interactions, which creates an enthalpic penalty as the ion approaches the interface. Finally, we find that the fluctuation in the coordination number around water sheds new light on the observed entropic trends for both ions.

Multiscale reactive molecular dynamics

Many processes important to chemistry, materials science, and biology cannot be described without considering electronic and nuclear-level dynamics and their coupling to slower, cooperative motions of the system. These inherently multiscale problems require computationally efficient and accurate methods to converge statistical properties. In this paper, a method is presented that uses data directly from condensed phase ab initio simulations to develop reactive molecular dynamics models that do not require predefined empirical functions. Instead, the interactions used in the reactive model are expressed as linear combinations of interpolating functions that are optimized by using a linear least-squares algorithm. One notable benefit of the procedure outlined here is the capability to minimize the number of parameters requiring nonlinear optimization. The method presented can be generally applied to multiscale problems and is demonstrated by generating reactive models for the hydrated excess proton and hydroxide ion based directly on condensed phase ab initio molecular dynamics simulations. The resulting models faithfully reproduce the water-ion structural properties and diffusion constants from the ab initio simulations. Additionally, the free energy profiles for proton transfer, which is sensitive to the structural diffusion of both ions in water, are reproduced. The high fidelity of these models to ab initio simulations will permit accurate modeling of general chemical reactions in condensed phase systems with computational efficiency orders of magnitudes greater than currently possible with ab initio simulation methods, thus facilitating a proper statistical sampling of the coupling to slow, large-scale motions of the system.

Insights into the transport of aqueous quaternary ammonium cations: a combined experimental and computational study.

This study focuses on understanding the relative effects of ammonium substituent groups (we primarily consider tetramethylammonium, benzyltrimethylammonium, and tetraethylammonium cations) and anion species (OH(-), HCO3(-), CO3(2-), Cl(-), and F(-)) on ion transport by combining experimental and computational approaches. We characterize transport experimentally using ionic conductivity and self-diffusion coefficients measured from NMR. These experimental results are interpreted using simulation methods to describe the transport of these cations and anions considering the effects of the counterion. It is particularly noteworthy that we directly probe cation and anion diffusion with pulsed gradient stimulated echo NMR and molecular dynamics simulations, corroborating these methods and providing a direct link between atomic-resolution simulations and macroscale experiments. By pairing diffusion measurements and simulations with residence times, we were able to understand the interplay between short-time and long-time dynamics with ionic conductivity. With experiment, we determined that solutions of benzyltrimethylammonium hydroxide have the highest ionic conductivity (0.26 S/cm at 65 °C), which appears to be due to differences for the ions in long-time diffusion and short-time water caging. We also examined the effect of CO2 on ionic conductivity in ammonium hydroxide solutions. CO2 readily reacts with OH(-) to form HCO(-)3 and is found to lower the solution ionic conductivity by almost 50%.

Optimizing the switching function for nonequilibrium free-energy calculations: An on-the-fly approach

Using nonequilibrium switching simulations to determine the free-energy difference between two thermodynamic states has gained tremendous popularity since Jarzynskis identity was proposed. The efficiency of a nonequilibrium switching simulation depends on the switching function. A well selected switching function can significantly minimize the associated dissipative work and reduce the computational cost of nonequilibrium free-energy simulations. In this paper, a method for estimating an efficient switching function during a nonequilibrium free-energy simulation is presented. The switching rate depends on the fluctuation of the fictitious force and a relaxation time. This method is similar to a prior method described by de Koning [J. Chem. Phys. 122, 104106 (2005)], except in our approach the switching rate is determined on-the-fly without the need for trial pulls. Our method can be easily incorporated into any existing implementation of the nonequilibrium switching method. The on-the-fly approach was used to determine the transformation free energy between two types of Einstein crystals and the isothermal free energy of expansion of a van der Waals gas. For both of the test cases, our on-the-fly method is found to provide a switching function much more superior than the standard one.