Explicitly Correlated Gaussian Basis Approach to Periodic Systems

Abstract

Closed-form expressions for all matrix elements required for variational calculation of the electronic structure of periodic solids have been derived using a basis of explicitly correlated Gaussians (ECGs). Periodic basis functions are constructed by summing shifted correlated Gaussians over all composite lattice translations, where a generalized unfolding theorem reduces the resulting double lattice sum to a single sum through a unified computational framework for overlap, kinetic energy, and Coulomb potential operators. The formalism has been validated through application to an infinite one-dimensional hydrogen chain, where the ground-state energy per atom computed in the thermodynamic limit is shown to agree with finite-chain results extrapolated by other many-body methods.