Equivariant analytical mapping of first principles Hamiltonians to accurate and transferable materials models

Abstract We propose a scheme to construct predictive models for Hamiltonian matrices in atomic orbital representation from ab initio data as a function of atomic and bond environments. The scheme goes beyond conventional tight binding descriptions as it represents the ab initio model to full order, rather than in two-centre or three-centre approximations. We achieve this by introducing an extension to the atomic cluster expansion (ACE) descriptor that represents Hamiltonian matrix blocks that transform equivariantly with respect to the full rotation group. The approach produces analytical linear models for the Hamiltonian and overlap matrices. Through an application to aluminium, we demonstrate that it is possible to train models from a handful of structures computed with density functional theory, and apply them to produce accurate predictions for the electronic structure. The model generalises well and is able to predict defects accurately from only bulk training data.