How close are the classical two-body potentials to ab initio calculations? Insights from linear machine learning based force matching.

In this work, we propose a linear machine learning force matching approach that can directly extract pair atomic interactions from ab initio calculations in amorphous structures. The local feature representation is specifically chosen to make the linear weights a force field as a force/potential function of the atom pair distance. Consequently, this set of functions is the closest representation of the ab initio forces, given the two-body approximation and finite scanning in the configurational space. We validate this approach in amorphous silica. Potentials in the new force field (consisting of tabulated Si-Si, Si-O, and O-O potentials) are significantly different than existing potentials that are commonly used for silica, even though all of them produce the tetrahedral network structure and roughly similar glass properties. This suggests that the commonly used classical force fields do not offer fundamentally accurate representations of the atomic interaction in silica. The new force field furthermore produces a lower glass transition temperature (Tg ∼ 1800 K) and a positive liquid thermal expansion coefficient, suggesting the extraordinarily high Tg and negative liquid thermal expansion of simulated silica could be artifacts of previously developed classical potentials. Overall, the proposed approach provides a fundamental yet intuitive way to evaluate two-body potentials against ab initio calculations, thereby offering an efficient way to guide the development of classical force fields.

Surface Diffusion Is Controlled by Bulk Fragility across All Glass Types.

Surface diffusion is vastly faster than bulk diffusion in some glasses, but only moderately enhanced in others. We show that this variation is closely linked to bulk fragility, a common measure of how quickly dynamics is excited when a glass is heated to become a liquid. In fragile molecular glasses, surface diffusion can be a factor of 10^{8} faster than bulk diffusion at the glass transition temperature, while in the strong system SiO_{2}, the enhancement is a factor of 10. Between these two extremes lie systems of intermediate fragility, including metallic glasses and amorphous selenium and silicon. This indicates that stronger liquids have greater resistance to dynamic excitation from bulk to surface and enables prediction of surface diffusion, surface crystallization, and formation of stable glasses by vapor deposition.

Decoding ionic conductivity and reordering in cation-disordered pyrochlores.

The ordered structure A2B2O6O' in pyrochlores engenders twin rows of inequivalent anion sublattices each centred on alternating cations. While it is known that cation antisite disorder augments the ionic conductivity by several orders of magnitude, the local cation environment around the anions and the dynamic anion reordering during the cation disordering are not well-elucidated. Using atomistic simulations on Gd2Zr2O7, we first show that the anions engage in concerted hops to the neighbouring tetrahedral sites mostly along with the 〈1 0 0〉 direction while completely avoiding the octahedral sites. While the initially vacant 8a sites start accommodating oxygen ions with increasing cation disorder, they show noticeable reluctance even at significant levels of disorder. We have also tracked both the distribution of available oxygen sites following random cation disorder, which is dependent only on cation disordering, and the probability of occupation of these sites. Interestingly, the available oxygen sites show a non-monotonic dependence on the number of B ions in the nearest neighbouring shell while the occupation probability of all the available oxygen sites increases monotonically. A tetrahedral oxygen site thus has a better probability of being occupied when it has a greater number of second neighbour B ions. This article is part of the Theo Murphy meeting issue 'Understanding fast-ion conduction in solid electrolytes'.

Fast Surface Dynamics on a Metallic Glass Nanowire.

The dynamics near the surface of glasses can be much faster than in the bulk. We studied the surface dynamics of a Pt-based metallic glass using electron correlation microscopy with sub-nanometer resolution. Our studies show an ∼20 K suppression of the glass transition temperature at the surface. The enhancement in surface dynamics is suppressed by coating the metallic glass with a thin layer of amorphous carbon. Parallel molecular dynamics simulations on Ni80P20 show a similar temperature suppression of the surface glass transition temperature and that the enhanced surface dynamics are arrested by a capping layer that chemically binds to the glass surface. Mobility in the near-surface region occurs via atomic caging and hopping, with a strong correlation between slow dynamics and high cage-breaking barriers and stringlike cooperative motion. Surface and bulk dynamics collapse together as a function of temperature rescaled by their respective glass transition temperatures.

Factors correlating to enhanced surface diffusion in metallic glasses.

The enhancement of surface diffusion (DS) over the bulk (DV) in metallic glasses (MGs) is well documented and likely to strongly influence the properties of glasses grown by vapor deposition. Here, we use classical molecular dynamics (MD) simulations to identify different factors influencing the enhancement of surface diffusion in MGs. MGs have a simple atomic structure and belong to the category of moderately fragile glasses that undergo pronounced slowdown of bulk dynamics with cooling close to the glass transition temperature (Tg). We observe that DS exhibits a much more moderate slowdown compared to DV when approaching Tg, and DS/DV at Tg varies by two orders of magnitude among the MGs investigated. We demonstrate that both the surface energy and the fraction of missing bonds for surface atoms show good correlation to DS/DV, implying that the loss of nearest neighbors at the surface directly translates into higher mobility, unlike the behavior of network-bonded and hydrogen-bonded organic glasses. Fragility, a measure of the slowdown of bulk dynamics close to Tg, also correlates to DS/DV, with more fragile systems having larger surface enhancement of mobility. The deviations observed in the fragility-DS/DV relationship are shown to be correlated to the extent of segregation or depletion of the mobile element at the surface. Finally, we explore the relationship between the diffusion pre-exponential factor (D0) and the activation energy (Q) and compare it to a ln(D0)-Q correlation previously established for bulk glasses, demonstrating similar correlations from MD as in the experiments and that the surface and bulk have very similar ln(D0)-Q correlations.

Low Dimensional String-like Relaxation Underpins Superionic Conduction in Fluorites and Related Structures.

Among the superionic conductors that show a Faraday transition - the continuous increase in the ionic conductivity over a range of temperatures - the fluorite structures have enjoyed incisive examinations over the past four decades; yet the fundamental nature of superionicity has remained largely inconclusive. Departing from the traditional quasi-static defect framework, we provide weighty evidence for string-like dynamical structures that govern the fast ion conduction process in fluorites. We show that lower temperatures encourage the growth of longer but slowly relaxing strings and vice-versa - a direct manifestation of heterogeneous dynamics. Remarkably, the ionic conductivity is inversely correlated to the lifetime of the ions that participate in the strings and not explicitly to the ion population. Our analysis methodology, which resolves a long-standing disagreement on defect structures and the mechanism of ionic transport in fcc fluorite structures, is well-positioned to describe the dynamics of low dimensional conduction in a larger class of superionic conductors.

Mobility propagation and dynamic facilitation in superionic conductors.

In an earlier work [V. A. Annamareddy et al., Phys. Rev. E 89, 010301(R) (2014)], we showed the manifestation of dynamical heterogeneity (DH)-the presence of clustered mobile and immobile regions-in UO2, a model type II superionic conductor. In the current work, we demonstrate the mechanism of dynamic facilitation (DF) in two superionic conductors (CaF2 and UO2) using atomistic simulations. Using the mobility transfer function, DF is shown to vary non-monotonically with temperature with the intensity of DF peaking at temperatures close to the superionic transition temperature (Tλ). Both the metrics quantifying DH and DF show remarkable correspondence implying that DF, in the framework of kinematically constrained models, underpins the heterogeneous dynamics in type II superionic conductors.