DLPNO-MP2 with Periodic Boundary Conditions

Abstract

We present domain-based local pair natural orbital M{\o}ller--Plesset second order perturbation theory (DLPNO-MP2) with Born--von K{\'a}rm{\'a}n boundary (BvK) conditions. The approach is based on well-localised Wannier functions in a LCAO formalism and extends the molecular DLPNO-MP2 implementation Tubromole program package to periodic systems. The PNOs are formed through a PAO-OSV-PNO cascade, using BvK projected atomic orbitals and orbital specific virtuals as intermediaries in an analogous manner to the molecular scheme. Our chargeless and surface-dipole corrected local density fitting approach is shown to be numerically stable and to ensure convergent lattice summations over the periodic images for the two- and three-index Coulomb integrals. Through careful benchmarking, we show that the DLPNO approximations in the BvK-DLPNO-MP2 methods are entirely consistent with those of molecular DLPNO-MP2 calculations, and with an alternative periodic approach Megacell-DLPNO-MP2, reported in Paper II of this series. Smooth convergence to the canonical correlation energy with tightening PNO threshold is observed. Reference MP2 correlation energies are provided for a set of 2D and 3D periodic systems using a triple-zeta basis and supercell sizes up to 11$\times$11 and 7$\times$7$\times$7.