Linear scaling computation of the Hartree–Fock exchange matrix

Abstract
Thresholding criteria are introduced that enforce locality of exchange interactions in Cartesian Gaussian‐based Hartree–Fock calculations. These criteria are obtained from an asymptotic form of the density matrix valid for insulating systems, and lead to a linear scaling algorithm for computation of the Hartree–Fock exchange matrix. Restricted Hartree–Fock/3‐21G calculations on a series of water clusters and polyglycine α‐helices are used to demonstrate the O(N) complexity of the algorithm, its competitiveness with standard direct self‐consistent field methods, and a systematic control of error in converged total energies.

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