Robust Estimation of Position-Dependent Anisotropic Diffusivity Tensors from Molecular Dynamics Trajectories.

Confinement breaks translational and rotational symmetry in materials and makes all physical properties functions of position. Such spatial variations are key to modulating material properties at the nanoscale, and characterizing them accurately is therefore an intense area of research in the molecular simulations community. This is relatively easy to accomplish for basic mechanical observables. Determining spatial profiles of transport properties, such as diffusivity, is, however, much more challenging, as it requires calculating position-dependent autocorrelations of mechanical observables. In our previous paper (Domingues, T.S.; Coifman, R.; Haji-Akbari, A. , , 5273 10.1021/acs.jpcb.3c00670), we analytically derive and numerically validate a set of filtered covariance estimators (FCEs) for quantifying spatial variations of the diffusivity tensor from stochastic trajectories. In this work, we adapt these estimators to extract diffusivity profiles from MD trajectories and validate them by applying them to a Lennard-Jones fluid within a slit pore. We find our MD-adapted estimator to exhibit the same qualitative features as its stochastic counterpart, as it accurately estimates the lateral diffusivity across the pore while systematically underestimating the normal diffusivity close to hard boundaries. We introduce a conceptually simple and numerically efficient correction scheme based on simulated annealing and diffusion maps to resolve the latter artifact and obtain normal diffusivity profiles that are consistent with the self-part of the van Hove correlation functions. Our findings demonstrate the potential of this MD-adapted estimator in accurately characterizing spatial variations of diffusivity in confined materials.