Alex Squires (@agsquires.bsky.social)

Accurate Estimation of Diffusion Coefficients and their Uncertainties from Computer Simulation Self-diffusion coefficients, D*, are routinely estimated from molecular dynamics simulations by fitting a linear model to the observed mean squared displacements (MSDs) of mobile species. MSDs derived from simulations exhibit statistical noise that causes uncertainty in the resulting estimate of D*. An optimal scheme for estimating D* minimizes this uncertainty, i.e., it will have high statistical efficiency, and also gives an accurate estimate of the uncertainty itself. We present a scheme for estimating D* from a single simulation trajectory with a high statistical efficiency and accurately estimating the uncertainty in the predicted value. The statistical distribution of MSDs observable from a given simulation is modeled as a multivariate normal distribution using an analytical covariance matrix for an equivalent system of freely diffusing particles, which we parametrize from the available simulation data. We use Bayesian regression to sample the distribution of linear models that are compatible with this multivariate normal distribution to obtain a statistically efficient estimate of D* and an accurate estimate of the associated statistical uncertainty. https://doi.org/10.1021/acs.jctc.4c01249