We develop ab initio force fields for alkylimidazolium-based ionic liquids (ILs) that predict the density, heats of vaporization, diffusion, and conductivity that are in semiquantitative agreement with experimental data. These predictions are useful in light of the scarcity of and sometimes inconsistency in experimental heats of vaporization and diffusion coefficients. We illuminate physical trends in the liquid cohesive energy with cation chain length and anion. These trends are different than those based on the experimental heats of vaporization. Molecular dynamics prediction of the room temperature dynamics of such ILs is more difficult than is generally realized in the literature due to large statistical uncertainties and sensitivity to subtle force field details. We believe that our developed force fields will be useful for correctly determining the physics responsible for the structure/property relationships in neat ILs.

Quantifying ion association and collective dynamical processes in organic electrolytes is essential for fundamental property interpretation and optimization for electrochemical applications. The extent of ion correlation depends on both the ion concentration and dielectric strength of the solvent; ions may be largely uncorrelated in sufficiently high dielectric solvents at low concentration, but properties of concentrated electrolytes are dictated by correlated and collective ion processes. In this work, we utilize molecular dynamics simulations to characterize ion association and collective ion dynamics in organic electrolytes composed of binary mixtures of 1-butyl-3-] and 1,2-dichloroethane, acetone, acetonitrile, and water solvents. We illustrate different physical regimes of characteristically distinct ion correlation for the systematic range of electrolyte concentrations and solvent dielectric strengths. Dilute electrolytes composed of low-dielectric solvents exhibit significant counterion correlation in the form of ion-pairing and clustering driven by both weak screening and relatively low solvation energies. This regime is characterized by enhanced ion coordination numbers and near equality of cation and anion diffusion coefficients, despite the significantly different ion sizes. In contrast, ion correlation in highly concentrated electrolytes is dominated by the anti-correlated motion of both like-charge and opposite-charge ions, approaching neat ionic liquid behavior. We show that the cross-over of these correlation regimes is clearly illuminated by quantifying the fractional self and distinct contributions to the net ionic conductivity. For organic electrolytes composed of low-dielectric solvents, we conclude that significant ion correlation exists at all concentrations, but the nature of the correlation changes markedly from the dilute electrolyte to the pure ionic liquid limit.

Molecular dynamics study of ionic liquids (ILs) is a challenging task. While accurate fully polarizable atomistic models exist, they are computationally too demanding for routine use. Most nonpolarizable atomistic models predict diffusion constants that are much lower than experiment. Scaled charge atomistic models are cost-effective and give good results for single component ILs but are in qualitative error for the phase behavior of mixtures, due to inaccurate prediction of the IL cohesive energy. In this work, we present an alternative approach for developing computationally efficient models that importantly preserves both the correct dynamics and cohesive energy of the IL. Employing a "top-down" approach, a hierarchy of coarse-grained models for BMIM(+)BF4(-) are developed by systematically varying the polarization/atomic resolution of the distinct functional groups. Parametrization is based on symmetry-adapted perturbation theory (SAPT) calculations involving the homomolecular species; all cross interactions are obtained from mixing rules, and there are no adjustable parameters. We find that enhanced dynamics from a united-atom description counteracts the effect of reduced polarization, enabling computationally efficient models that exhibit quantitative agreement with experiment for both static and dynamic properties. We give explicit suggestions for reduced-description models that are computationally more efficient, more accurate, and more fundamentally sound than existing nonpolarizable atomistic models.

Cytochrome oxidase (CcO) is a transmembrane protein that uses the free energy of O reduction to generate the proton concentration gradient across the membrane. The regulation of competitive proton transfer pathways has been established to be essential to the vectorial transport efficiency of CcO, yet the underlying mechanism at the molecular level remains lacking. Recent studies have highlighted the potential importance of hydration-level change in an internal cavity that connects the proton entrance channel, the site of O reduction, and the putative proton exit route. In this work, we use atomistic molecular dynamics simulations to investigate the energetics and timescales associated with the volume fluctuation and hydration-level change in this central cavity. Extensive unrestrained molecular dynamics simulations (accumulatively [Formula: see text]4 [Formula: see text]s) and free energy computations for different chemical states of CcO support a model in which the volume and hydration level of the cavity are regulated by the protonation state of a propionate group of heme a and, to a lesser degree, the redox state of heme a and protonation state of Glu286. Markov-state model analysis of [Formula: see text]2-[Formula: see text]s trajectories suggests that hydration-level change occurs on the timescale of 100-200 ns before the proton-loading site is protonated. The computed energetic and kinetic features for the cavity wetting transition suggest that reversible hydration-level change of the cavity can indeed be a key factor that regulates the branching of proton transfer events and therefore contributes to the vectorial efficiency of proton transport.

Solid-state polymer electrolytes and high-concentration liquid electrolytes, such as water-in-salt electrolytes and ionic liquids, are emerging materials to replace the flammable organic electrolytes widely used in industrial lithium-ion batteries. Extensive efforts have been made to understand the ion transport mechanisms and optimize the ion transport properties. This perspective reviews the current understanding of the ion transport and polymer dynamics in liquid and polymer electrolytes, comparing the similarities and differences in the two types of electrolytes. Combining recent experimental and theoretical findings, we attempt to connect and explain ion transport mechanisms in different types of small-molecule and polymer electrolytes from a theoretical perspective, linking the macroscopic transport coefficients to the microscopic, molecular properties such as the solvation environment of the ions, salt concentration, solvent/polymer molecular weight, ion pairing, and correlated ion motion. We emphasize universal features in the ion transport and polymer dynamics by highlighting the relevant time and length scales. Several outstanding questions and anticipated developments for electrolyte design are discussed, including the negative transference number, control of ion transport through precision synthesis, and development of predictive multiscale modeling approaches.

Electrostatic interactions near surfaces and interfaces are ubiquitous in many fields of science. Continuum electrostatics predicts that ions will be attracted to conducting electrodes but repelled by surfaces with lower dielectric constant than the solvent. However, several recent studies found that certain “chaotropic” ions have similar adsorption behavior at air/water and graphene/water interfaces. Here we systematically study the effect of polarization of the surface, the solvent, and solutes on the adsorption of ions onto the electrode surfaces using molecular dynamics simulation. An efficient method is developed to treat an electrolyte system between two parallel conducting surfaces by exploiting the mirror-expanded symmetry of the exact image-charge solution. With neutral surfaces, the image interactions induced by the solvent dipoles and ions largely cancel each other, resulting in no significant net differences in the ion adsorption profile regardless of the surface polarity. Under an external electric field, the adsorption of ions is strongly affected by the surface polarization, such that the charge separation across the electrolyte and the capacitance of the cell is greatly enhanced with a conducting surface over a low-dielectric-constant surface. While the extent of ion adsorption is highly dependent on the electrolyte model (the polarizability of solvent and solutes, as well as the van der Waals radii), we find the effect of surface polarization on ion adsorption is consistent throughout different electrolyte models.

Cytochrome C oxidase plays a crucial role in cellular respiration and energy generation. It reduces O to water and uses the released free energy to move protons across mitochondrial and bacterial cell membranes adding to the essential electrochemical gradient. Energy storage requires that protons are taken up from the high pH, N-side and released to the low pH, P-side of the membrane. We identify a potential proton exit from a buried cluster of polar residues (the proton loading site) to the P-side of CcO via paths made up of waters and conserved residues. Two water cavities connect the proton exit pathway to the surface only when hydrated. Changing the degree of hydration may control otherwise energetically favorable proton backflow from the P-side.

An explicit treatment of electronic polarization is critically important to accurate simulations of highly charged or interfacial systems. Compared to the iterative self-consistent field (SCF) scheme, extended Lagrangian approaches are computationally more efficient for simulations that employ a polarizable force field. However, an appropriate thermostat must be chosen to minimize heat flow and ensure an equipartition of kinetic energy among all unconstrained system degrees of freedom. Here we investigate the effects of different thermostats on the simulation of condensed phase systems with the Drude polarizable force field using several examples that include water, NaCl/water, acetone, and an ionic liquid (IL) BMIM + /BF 4 − . We show that conventional dual-temperature thermostat schemes often suffer from violations of equipartitioning and adiabatic electronic state, leading to considerable errors in both static and dynamic properties. Heat flow from the real degrees of freedom to the Drude degrees of freedom leads to a steady temperature gradient and puts the system at an incorrect effective temperature. Systems with high-frequency internal degrees of freedom such as planar improper dihedrals or C−H bond stretches are most vulnerable; this issue has been largely overlooked in the literature because of the primary focus on simulations of rigid water molecules. We present a new temperature-grouped dual-Nose−Hoover thermostat, where the molecular center of mass translations are assigned to a temperature group separated from the rest degrees of freedom. We demonstrate that this scheme predicts correct static and dynamic properties for all the systems tested here, regardless of the thermostat coupling strength. This new thermostat has been implemented into the GPU-accelerated OpenMM simulation package and maintains a significant speedup relative to the SCF scheme.