Wavefunction-based periodic quantum chemistry
arXiv:2607.28554
The paper provides a tutorial on performing high‑accuracy quantum chemistry calculations for periodic (solid‑state) systems, covering mean‑field and correlated methods, basis sets, k‑point sampling, and techniques to reduce computational cost.
Abstract
High-accuracy molecular quantum chemistry offers a promising toolbox for applications to condensed-phase systems, but this field is difficult to enter due to its combination of topics from molecular quantum chemistry, solid-state physics, and numerical methods. Aiming to ease this transition, we present a comprehensive, pedagogical tutorial on periodic quantum chemistry calculations, using both mean-field and correlated theories. The subtleties of periodic Coulomb interactions are discussed in detail, focusing on the Ewald summation approach. We describe the two most popular periodic, one-electron basis functions---plane waves and periodic linear combinations of atomic orbitals---and we give formulas for all Hamiltonian integrals. Next, we explain the use of -point sampling as a symmetry adaptation of supercell basis functions and the associated savings in computational costs as well as the use of density fitting and related approximations to further reduce costs. We present the working equations of a few example periodic quantum chemistry methods, including Hartree-Fock theory, perturbation theory, and coupled-cluster theory, and we discuss their finite-size errors and convergence to the physically relevant thermodynamic limit. Finally, we briefly discuss local correlation and quantum embedding theories, which are especially appropriate for periodic systems due to their lattice translational symmetries.
22 pages, 6 figures