G-Quadruplex-Filtered Selective Ion-to-Ion Current Amplification for Non-Invasive Ion Monitoring in Real Time.

Living cells efflux intracellular ions for maintaining cellular life, so intravital measurements of specific ion signals are of significant importance for studying cellular functions and pharmacokinetics. In this work, de novo synthesis of artificial K+ -selective membrane and its integration with polyelectrolyte hydrogel-based open-junction ionic diode (OJID) is demonstrated, achieving a real-time K+ -selective ion-to-ion current amplification in complex bioenvironments. By mimicking biological K+ channels and nerve impulse transmitters, in-line K+ -binding G-quartets are introduced across freestanding lipid bilayers by G-specific hexylation of monolithic G-quadruplex, and the pre-filtered K+ flow is directly converted to amplified ionic currents by the OJID with a fast response time at 100 ms intervals. By the synergistic combination of charge repulsion, sieving, and ion recognition, the synthetic membrane allows K+ transport exclusively without water leakage; it is 250× and 17× more permeable toward K+ than monovalent anion, Cl- , and polyatomic cation, N-methyl-d-glucamine+ , respectively. The molecular recognition-mediated ion channeling provides a 500% larger signal for K+ as compared to Li+ (0.6× smaller than K+ ) despite the same valence. Using the miniaturized device, non-invasive, direct, and real-time K+ efflux monitoring from living cell spheroids is achieved with minimal crosstalk, specifically in identifying osmotic shock-induced necrosis and drug-antidote dynamics.

Sculpting In-plane Fractal Porous Patterns in Two-Dimensional MOF Nanocrystals for Photoelectrocatalytic CO2 Reduction.

Herein, by choosing few-nm-thin two-dimensional (2D) nanocrystals of MOF-5 containing in-planner square lattices as a modular platform, a crystal lattice-guided wet-chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)-shaped and fractal-patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical-shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion-limited etching process has been optimized to devise high-yield of size-tunable fractal-pores on the MOF surface that tenders for a compatibly high payload of catalytic ReI -complexes using the existing large edge area once modified into a free amine-group-exposed inner pore surface. Finally, on benefiting from the long-range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross-interface charge-transportation and well-exposure of immobilized ReI -catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO2 -to-CO reduction.

Predictive Molecular Models for Charged Materials Systems: From Energy Materials to Biomacromolecules.

Electrostatic interactions play a dominant role in charged materials systems. Understanding the complex correlation between macroscopic properties with microscopic structures is of critical importance to develop rational design strategies for advanced materials. But the complexity of this challenging task is augmented by interfaces present in the charged materials systems, such as electrode-electrolyte interfaces or biological membranes. Over the last decades, predictive molecular simulations that are founded in fundamental physics and optimized for charged interfacial systems have proven their value in providing molecular understanding of physicochemical properties and functional mechanisms for diverse materials. Novel design strategies utilizing predictive models have been suggested as promising route for the rational design of materials with tailored properties. Here, an overview of recent advances in the understanding of charged interfacial systems aided by predictive molecular simulations is presented. Focusing on three types of charged interfaces found in energy materials and biomacromolecules, how the molecular models characterize ion structure, charge transport, morphology relation to the environment, and the thermodynamics/kinetics of molecular binding at the interfaces is discussed. The critical analysis brings two prominent field of energy materials and biological science under common perspective, to stimulate crossover in both research field that have been largely separated.

Superionic Bifunctional Polymer Electrolytes for Solid-State Energy Storage and Conversion.

Achieving superionic conductivity from solid-state polymer electrolytes is an important task in the development of future energy storage and conversion technologies. Herein, a platform for innovative electrolyte technologies based on a bifunctional polymer, poly(3-hydroxy-4-sulfonated styrene) (PS-3H4S), is presented. By incorporating OH and SO3 H functional groups at adjacent positions in the styrene repeating unit, "intra-monomer" hydrogen bonds are formed to effectively weaken the electrostatic interactions of the SO3 - moieties in the polymer matrix with embedded ions, promoting rich structural and dynamic heterogeneity in the PS-3H4S electrolyte. Upon the incorporation of an ionic liquid, interconnected rod-like ion channels, which allow the decoupling of ion relaxation from polymer relaxation, are formed in the stiff motif of the polymeric domains passivated by interfacial ionic layers. This results in accelerated proton hopping through the glassy polymer matrix, and proton hopping becomes more pronounced at cryogenic temperatures down to -35 °C. The PS-3H4S/ionic liquid composite electrolytes exhibit a high ionic conductivity of 10-3 S cm-1 and high storage modulus of ≈100 MPa at 25 °C, and can be successfully applied in soft actuators and lithium-metal batteries.

De novo selected hACE2 mimics that integrate hotspot peptides with aptameric scaffolds for binding tolerance of SARS-CoV-2 variants.

The frequent occurrence of viral variants is a critical problem in developing antiviral prophylaxis and therapy; along with stronger recognition of host cell receptors, the variants evade the immune system-based vaccines and neutralizing agents more easily. In this work, we focus on enhanced receptor binding of viral variants and demonstrate generation of receptor-mimicking synthetic reagents, capable of strongly interacting with viruses and their variants. The hotspot interaction of viruses with receptor-derived short peptides is maximized by aptamer-like scaffolds, the compact and stable architectures of which can be in vitro selected from a myriad of the hotspot peptide-coupled random nucleic acids. We successfully created the human angiotensin-converting enzyme 2 (hACE2) receptor-mimicking hybrid ligand that recruits the hACE2-derived receptor binding domain-interacting peptide to directly interact with a binding hotspot of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Experiencing affinity boosting by ~500% to Omicron, the de novo selected hACE2 mimic exhibited a great binding tolerance to all SARS-CoV-2 variants of concern.

Chain flexibility of medicinal lipids determines their selective partitioning into lipid droplets.

In guiding lipid droplets (LDs) to serve as storage vessels that insulate high-value lipophilic compounds in cells, we demonstrate that chain flexibility of lipids determines their selective migration in intracellular LDs. Focusing on commercially important medicinal lipids with biogenetic similarity but structural dissimilarity, we computationally and experimentally validate that LD remodeling should be differentiated between overproduction of structurally flexible squalene and that of rigid zeaxanthin and ß-carotene. In molecular dynamics simulations, worm-like flexible squalene is readily deformed to move through intertwined chains of triacylglycerols in the LD core, whereas rod-like rigid zeaxanthin is trapped on the LD surface due to a high free energy barrier in diffusion. By designing yeast cells with either much larger LDs or with a greater number of LDs, we observe that intracellular storage of squalene significantly increases with LD volume expansion, but that of zeaxanthin and ß-carotene is enhanced through LD surface broadening; as visually evidenced, the outcomes represent internal penetration of squalene and surface localization of zeaxanthin and ß-carotene. Our study shows the computational and experimental validation of selective lipid migration into a phase-separated organelle and reveals LD dynamics and functionalization.

Metastable hexagonal close-packed palladium hydride in liquid cell TEM.

Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.

Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces.

Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as "dead zone" to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.

Au/Pt-Egg-in-Nest Nanomotor for Glucose-Powered Catalytic Motion and Enhanced Molecular Transport to Living Cells.

Nanostructures converting chemical energy to mechanical work by using benign metabolic fuels, have huge implications in biomedical science. Here, we introduce Au/Pt-based Janus nanostructures, resembling to "egg-in-nest" morphology (Au/Pt-ENs), showing enhanced motion as a result of dual enzyme-relay-like catalytic cascade in physiological biomedia, and in turn showing molecular-laden transport to living cells. We developed dynamic-casting approach using silica yolk-shell nanoreactors: first, to install a large Au-seed fixing the silica-yolk aside while providing the anisotropically confined concave hollow nanospace to grow curved Pt-dendritic networks. Owing to the intimately interfaced Au and Pt catalytic sites integrated in a unique anisotropic nest-like morphology, Au/Pt-ENs exhibited high diffusion rates and displacements as the result of glucose-converted oxygen concentration gradient. High diffusiophoresis in cell culture media increased the nanomotor-membrane interaction events, in turn facilitated the cell internalization. In addition, the porous network of Au/Pt-ENs facilitated the drug-molecule cargo loading and delivery to the living cells.

Image-charge effects on ion adsorption near aqueous interfaces.

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.

Ion transport in small-molecule and polymer electrolytes.

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.

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids.

We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids," a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

Identifying the proton loading site cluster in the ba3 cytochrome c oxidase that loads and traps protons.

Cytochrome c Oxidase (CcO) is the terminal electron acceptor in aerobic respiratory chain, reducing O2 to water. The released free energy is stored by pumping protons through the protein, maintaining the transmembrane electrochemical gradient. Protons are held transiently in a proton loading site (PLS) that binds and releases protons driven by the electron transfer reaction cycle. Multi-Conformation Continuum Electrostatics (MCCE) was applied to crystal structures and Molecular Dynamics snapshots of the B-type Thermus thermophilus CcO. Six residues are identified as the PLS, binding and releasing protons as the charges on heme b and the binuclear center are changed: the heme a3 propionic acids, Asp287, Asp372, His376 and Glu126B. The unloaded state has one proton and the loaded state two protons on these six residues. Different input structures, modifying the PLS conformation, show different proton distributions and result in different proton pumping behaviors. One loaded and one unloaded protonation states have the loaded/unloaded states close in energy so the PLS binds and releases a proton through the reaction cycle. The alternative proton distributions have state energies too far apart to be shifted by the electron transfers so are locked in loaded or unloaded states. Here the protein can use active states to load and unload protons, but has nearby trapped states, which stabilize PLS protonation state, providing new ideas about the CcO proton pumping mechanism. The distance between the PLS residues Asp287 and His376 correlates with the energy difference between loaded and unloaded states.

Proper Thermal Equilibration of Simulations with Drude Polarizable Models: Temperature-Grouped Dual-Nosé-Hoover Thermostat.

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+/BF4-. 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-Nosé-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.

Ion Correlation and Collective Dynamics in BMIM/BF4-Based Organic Electrolytes: From Dilute Solutions to the Ionic Liquid Limit.

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-methylimidazolium tetrafluoroborate [BMIM+][BF4-] and 1,2-dichloroethane, acetone, acetonitrile, and water solvents. We illustrate different physical regimes of characteristically distinct ion correlations 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.

Network analysis of a proposed exit pathway for protons to the P-side of cytochrome c oxidase.

Cytochrome c Oxidase (CcO) reduces O2, the terminal electron acceptor, to water in the aerobic, respiratory electron transport chain. The energy released by O2 reductions is stored by removing eight protons from the high pH, N-side, of the membrane with four used for chemistry in the active site and four pumped to the low pH, P-side. The proton transfers must occur along controllable proton pathways that prevent energy dissipating movement towards the N-side. The CcO N-side has well established D- and K-channels to deliver protons to the protein interior. The P-side has a buried core of hydrogen-bonded protonatable residues designated the Proton Loading Site cluster (PLS cluster) and many protonatable residues on the P-side surface, providing no obvious unique exit. Hydrogen bond pathways were identified in Molecular Dynamics (MD) trajectories of Rb. sphaeroides CcO prepared in the PR state with the heme a3 propionate and Glu286 in different protonation states. Grand Canonical Monte Carlo sampling of water locations, polar proton positions and residue protonation states in trajectory snapshots identify a limited number of water mediated, proton paths from PLS cluster to the surface via a (P-exit) cluster of residues. Key P-exit residues include His93, Ser168, Thr100 and Asn96. The hydrogen bonds between PLS cluster and P-exit clusters are mediated by a water wire in a cavity centered near Thr100, whose hydration can be interrupted by a hydrophobic pair, Leu255B (near CuA) and Ile99. Connections between the D channel and PLS via Glu286 are controlled by a second, variably hydrated cavity. SIGNIFICANCE STATEMENT: Cytochrome C oxidase plays a crucial role in cellular respiration and energy generation. It reduces O2 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.

Ab Initio Force Fields for Organic Anions: Properties of [BMIM][TFSI], [BMIM][FSI], and [BMIM][OTf] Ionic Liquids.

Room-temperature ionic liquids (ILs) composed of organic anions bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and trifluoromethanesulfonate (OTf) exhibit interesting physical properties and are important for many electrochemical applications. TFSI and FSI form "hydrophobic" ILs, immiscible with water but miscible with many organic solvents and polymers; for computer simulation studies, it is thus essential to develop force fields for these anions that are transferable among this wide variety of chemical environments. In this work, we develop entirely ab initio force fields for the TFSI, FSI, and OTf anions and predict the properties of corresponding 1-butyl-3-methylimidazolium ILs. We discuss important subtleties in the force field development related to accurately modeling conformational flexibility, that is, relaxed torsional profiles and intramolecular electrostatic interactions. The TFSI anions have notable conformational flexibility in the IL, and we predict approximately 70% cisoid and 20% transoid conformations, which is largely driven by cation/anion ion-pair interactions and is opposite to the trend expected from the anion ab initio potential energy surface. The favorable interactions between the cation and cisoid TFSI conformations result in a shoulder in the cation/anion radial distribution function at short distances, whereas interconversion between cisoid and transoid conformations occurs on a commensurate time scale as ion diffusion processes. In addition to this physical insight on anion effects, we expect that these force fields will have important applications for studying a variety of complex electrolyte systems.

Cavity hydration dynamics in cytochrome c oxidase and functional implications.

Cytochrome c oxidase (CcO) is a transmembrane protein that uses the free energy of O2 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 O2 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 a3 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.

Ab Initio Force Fields for Imidazolium-Based Ionic Liquids.

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.

First-Principles United Atom Force Field for the Ionic Liquid BMIM(+)BF4(-): An Alternative to Charge Scaling.

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.