Low-order scaling local electron correlation methods. I. Linear scaling local MP2

Abstract

A new implementation of local second-order Mo/ller-Plesset perturbation theory (LMP2) is presented for which asymptotically all computational resources (CPU, memory, and disk) scale only linearly with the molecular size. This is achieved by (i) using orbital domains for each electron pair that are independent of molecular size; (ii) classifying the pairs according to a distance criterion and neglecting very distant pairs; (iii) treating distant pairs by a multipole approximation, and (iv) using efficient prescreening algorithms in the integral transformation. The errors caused by the various approximations are negligible. LMP2 calculations on molecules including up to 500 correlated electrons and over 1500 basis functions in C1 symmetry are reported, all carried out on a single low-cost personal computer.