2025/07/13 by Nejad, Arman, Zhu, Andrew, Sorathia, Kesha +1 · 1 citation
#Chemical Physics (physics.chem-ph) #Computational Physics (physics.comp-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci)
paper · doi:10.48550/arxiv.2507.09810
We present domain-based local pair natural orbital Møller--Plesset second order perturbation theory (DLPNO-MP2) with Born--von Kármán 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 11×11 and 7×7×7.