Predicting the electronic density response of condensed-phase systems to electric field perturbations

Abstract

We present a local and transferable machine-learning approach capable of predicting the real-space density response of both molecules and periodic systems to homogeneous electric fields. The new method, Symmetry-Adapted Learning of Three-dimensional Electron Responses (SALTER), builds on the symmetry-adapted Gaussian process regression symmetry-adapted learning of three-dimensional electron densities framework. SALTER requires only a small, but necessary, modification to the descriptors used to represent the atomic environments. We present the performance of the method on isolated water molecules, bulk water, and a naphthalene crystal. Root mean square errors of the predicted density response lie at or below 10% with barely more than 100 training structures. Derived polarizability tensors and even Raman spectra further derived from these tensors show good agreement with those calculated directly from quantum mechanical methods. Therefore, SALTER shows excellent performance when predicting derived quantities, while retaining all of the information contained in the full electronic response. Thus, this method is capable of predicting vector fields in a chemical context and serves as a landmark for further developments.