Sensitivity Analysis for ReaxFF Reparametrization Using the Hilbert–Schmidt Independence Criterion

M. Freitas Gustavo, M. Hellström, T. Verstraelen
Journal of Chemical Theory and Computation
19, 9, 2557-2573


We apply a global sensitivity method, the Hilbert− Schmidt independence criterion (HSIC), to the reparametrization of a Zn/S/H ReaxFF force field to identify the most appropriate parameters for reparametrization. Parameter selection remains a challenge in this context, as high-dimensional optimizations are prone to overfitting and take a long time but selecting too few parameters leads to poor-quality force fields. We show that the HSIC correctly and quickly identifies the most sensitive parameters and that optimizations done using a small number of sensitive parameters outperform those done using a higher-dimensional reasonable-user parameter selection. Optimizations using only sensitive parameters (1) converge faster, (2) have loss values comparable to those found with the naive selection, (3) have similar accuracy in validation tests, and (4) do not suffer from problems of overfitting. We demonstrate that an HSIC global sensitivity is a cheap optimization preprocessing step that has both qualitative and quantitative benefits which can substantially simplify and speed up ReaxFF reparametrizations.