A scalable and accurate algorithm for the computation of Hartree-Fock exchange

Hartree-Fock exchange and hybrid density functionals have recently attracted renewed interest in electronic structure theory for the description of periodic systems, overcoming some of the limitations of local and semi-local approximations of density-functional theory (OFT). However, their use in plane-wave calculations for extended systems remains limited by poor convergence behavior regarding Brillouin-zone sampling and by a high overall computational cost. We present a computational approach that achieves quadratic convergence of exchange integrals with respect to Brillouin zone discretization, while using a compact representation of the exchange operator during non-self-consistent iterations. The computational cost is mitigated by an efficient parallel implementation. The method is applied to computations of Hartree-Fock and hybrid OFT (PBE0) band structures and structural parameters for bulk silicon and diamond. (C) 2010 Elsevier B.V. All rights reserved.