We propose a new scheme to parameterize effective potentials that can be used to simulate atomic systems such as oxide glasses. As input data for the optimization, we use the radial distribution functions of the liquid and the vibrational density of state of the glass, both obtained from ab-initio simulations, as well as experimental data on the pressure dependence of the density of the glass. For the case of silica, we find that this new scheme facilitates finding pair potentials that are significantly more accurate than previous ones even if the functional form is the same, thus demonstrating that even simple two-body potentials can be superior to more complex three-body potentials. We have tested the new potential by calculating the pressure dependence of the elastic moduli and find a good agreement with the corresponding experimental data.

We apply a recently developed optimization scheme to obtain effective potentials for alkali and alkaline-earth aluminosilicate glasses that contains lithium, sodium, potassium, or calcium as modifiers. As input data for the optimization, we used the radial distribution functions of the liquid at high temperature generated by means of ab initio molecular dynamics simulations and density and elastic modulus of glass at room temperature from experiments. The new interaction potentials are able to reproduce reliably the structure and various mechanical and vibrational properties over a wide range of compositions for binary silicates. We have tested these potentials for various ternary systems and find that they are transferable and can be mixed, thus allowing to reproduce and predict the structure and properties of multi-component glasses.

We adapt and apply a recently developed optimization scheme used to obtain effective potentials for aluminosilicate glasses to include the network former boron into the interaction parameter set. As input data for the optimization, we used the radial distribution functions of the liquid at high temperature generated by ab initio molecular dynamics simulations, and density, coordination and elastic modulus of glass at room temperature from experiments. The new interaction potentials are shown to reproduce reliably the structure, coordination and mechanical properties over a wide range of compositions for binary alkali borates. Furthermore, the transferability of these new interaction parameters allows mixing to reliably reproduce properties of various boroaluminate and borosilicate glasses. † Corresponding author. E-mail address: huangL5@rpi.edu (L. Huang). Potential and cost functionSimilar to our previous work on silica glass and aluminosilicate glasses 27,28 , we use the Buckingham potential functional form 31 for short-range interactions and the Wolf truncation method 32,33 to evaluate the Coulombic interactions.

Polymer electrolytes mitigate safety concerns surrounding flammable liquid electrolytes in lithium-ion batteries. Poly(ethylene oxide) (PEO) electrolytes demonstrate viable conductivity values (∼1 × 10 −3 S/ cm) at elevated temperatures (>70 °C) but a relatively low Li + current fraction (≤0.2) because strong Li + coordination inhibits cation mobility. We have developed a series of polyacetal electrolytes by systematically varying methylene oxide (MO) and ethylene oxide (EO) units in the polymer backbone. These materials maintain high oxygen-to-carbon ratios like PEO but offer improved ion transport, revealing trends of decreasing conductivity and increasing current fraction with respect to polymer composition. In particular, the increasing current fraction measured via the Bruce−Vincent method suggests that MO units improve Li + mobility relative to anion mobility. We calculate an overall efficacy (product of conductivity and current fraction) for each polymer/salt composition and identify two polymersP(EO-MO) and P(EO-2MO)that outperform PEO at high and low salt concentrations, respectively.

The success of polyethylene oxide (PEO) in solid-state polymer electrolytes for lithium-ion batteries is well established. Recently, in order to understand this success and to explore possible alternatives, we studied polyacetal electrolytes to deepen the understanding of the effect of the local chemical structure on ion transport. Advanced molecular dynamics techniques using newly developed, tailored interaction potentials have helped elucidate the various coordination environments of ions in these systems. In particular, the competition between cation−anion pairing and coordination by the polymer has been explored using freeenergy sampling (metadynamics). At equivalent reduced temperatures, with respect to the polymer-specific glass-transition temperature, two-dimensional free-energy plots reveal the existence of multiple coordination environments for the lithium (Li) ions in these systems and their relative stabilities. Furthermore, we observe that the Li-ion movement in PEO follows a serial, stepwise pathway when moving from one coordination state to another, whereas this happens in a more continuous and concerted fashion in a polyacetal such as poly(1,3-dioxalane) [P(EO-MO)]. The implication is that interconversion between coordination states of the Li ions may be easier in P(EO-MO). However, the overarching observation from our free-energy analysis is that Li-ion coordination is dominated by the polymer (in either case) and contact-ion pairs are rare. We rationalize the observed higher increase in glasstransition temperature (T g ) with salt loading in polyacetals as due to intermolecular Li-ion coordination involving multiple polymer chains, rather than just one chain for PEO-based electrolytes. This interchain coupling in the polyacetals, resulting in the higher T g , works against any gains due to variations in Li-ion coordination that might enhance transport processes over PEO. Further research is required to overcome the interdependence between local coordination and macroscopic properties to compete with PEO electrolytes at the same absolute working temperature. 36 through the free volume of the polymers assisted by the 37 segmental motion, with reasonable conductivity possible above 38 the glass-transition temperature. 6 Therefore, effective dissolu-39 tion of the cations and a low glass-transition temperature are 40 key to good ionic properties in these systems. 13 Unfortunately, 41 slow ionic conductivities and low transference numbers in

Polyacetal electrolytes have been demonstrated as promising alternatives to liquid electrolytes and PEO for rechargeable lithium-ion batteries; however, the relationship between polymer structure and ion motion is difficult to characterize. Here, we study structure-property trends in ion diffusion with respect to polymer composition for a systematic series of five polyacetals with varying ratios of ethylene oxide (EO) to methylene oxide (MO) units, denoted P(xEO-yMO), and PEO. We first use 7 Li and 19 F pulsed-field-gradient NMR spectroscopy to measure cation and anion self-diffusion, respectively, in polymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt mixtures. At 90 °C, we observe modest changes in Li + diffusivity across all polymer compositions while anion (TFSI − ) self-diffusion coefficients decrease significantly with increasing MO content. At a given reduced temperature (T − Tg), all polyacetal electrolytes exhibit faster Li + self-diffusion than PEO. Intriguingly, P(EO-MO) and P(EO-2MO) also show slower TFSI − anion self-diffusion than PEO at a given reduced temperature. Molecular dynamics simulations reveal that shorter distances between acetal oxygen atoms (O-CH2-O) compared to ether oxygens (O-CH2-CH2-O) promote more diverse, often asymmetric, Li + coordination environments. Raman spectra reveal that anion-rich ion clusters in P(EO-MO) and P(EO-2MO) lead to decreased anion diffusivity, which along with increased cation diffusivity, elucidate the viability of polyacetals as high-performance polymer electrolytes.

Experimental studies have shown that glass systems with high boron content exhibit superior crack resistance under sharp contact loading. However, the underlying mechanism is still not fully understood. In this context, we carried out classical molecular dynamics simulations on sodium aluminosilicate and sodium aluminoborate systems to investigate the effect of boron on the response of glass to nanoindentation. A rigid V-shaped indenter is used to indent the glass sample with a fixed loading rate, during which the indenter interacts with the glass via a repulsive force field. The indenter angle and tip radius are varied to study the effect of indenter sharpness, as what has been done in experiments. These simulated nanoindentation tests reveal how the stress/strain field and the glass structure evolve with deformation underneath the indenter. It was found that a large number of boron atoms in the plastic zone change from three- to fourfold coordination during the loading process, and most of them revert back to the threefold coordination state during the unloading process. Our study shows that this “reversible” boron coordination change plays a critical role in increasing the damage resistance of glass.

The success of polyethylene oxide (PEO) in solid-state polymer electrolytes for lithium-ion batteries is well established. Recently, in order to understand this success and to explore possible alternatives, we studied polyacetal electrolytes to deepen the understanding of the effect of the local chemical structure on ion transport. Advanced molecular dynamics techniques using newly developed, tailored interaction potentials have helped elucidate the various coordination environments of ions in these systems. In particular, the competition between cation−anion pairing and coordination by the polymer has been explored using freeenergy sampling (metadynamics). At equivalent reduced temperatures, with respect to the polymer-specific glass-transition temperature, two-dimensional free-energy plots reveal the existence of multiple coordination environments for the lithium (Li) ions in these systems and their relative stabilities. Furthermore, we observe that the Li-ion movement in PEO follows a serial, stepwise pathway when moving from one coordination state to another, whereas this happens in a more continuous and concerted fashion in a polyacetal such as poly(1,3-dioxalane) [P(EO-MO)]. The implication is that interconversion between coordination states of the Li ions may be easier in P(EO-MO). However, the overarching observation from our free-energy analysis is that Li-ion coordination is dominated by the polymer (in either case) and contact-ion pairs are rare. We rationalize the observed higher increase in glasstransition temperature (T g ) with salt loading in polyacetals as due to intermolecular Li-ion coordination involving multiple polymer chains, rather than just one chain for PEO-based electrolytes. This interchain coupling in the polyacetals, resulting in the higher T g , works against any gains due to variations in Li-ion coordination that might enhance transport processes over PEO. Further research is required to overcome the interdependence between local coordination and macroscopic properties to compete with PEO electrolytes at the same absolute working temperature. 36 through the free volume of the polymers assisted by the 37 segmental motion, with reasonable conductivity possible above 38 the glass-transition temperature. 6 Therefore, effective dissolu-39 tion of the cations and a low glass-transition temperature are 40 key to good ionic properties in these systems. 13 Unfortunately, 41 slow ionic conductivities and low transference numbers in