An efficient linear scaling procedure for constructing localized orbitals of large molecules based on the one-particle density matrix

Abstract

We have developed a linear-scaling algorithm for obtaining the Boys localized molecular orbitals from the one-particle density matrix. The algorithm is made up of two steps: the Cholesky decomposition of the density matrix to obtain Cholesky molecular orbitals and the subsequent Boys localization process. Linear-scaling algorithms have been proposed to achieve linear-scaling calculations of these two steps, based on the sparse matrix technique and the locality of the Cholesky molecular orbitals. The present algorithm has been applied to compute the Boys localized orbitals in a number of systems including α-helix peptides, water clusters, and protein molecules. Illustrative calculations demonstrate that the computational time of obtaining Boys localized orbitals with the present algorithm is asymptotically linear with increasing the system size.