Local Second-Order Møller-Plesset Theory with a Single Threshold Using Orthogonal Virtual Orbitals: Theory, Implementation, and Assessment

J Chem Theory Comput. 2023 Nov 14;19(21):7577-7591. doi: 10.1021/acs.jctc.3c00744. Epub 2023 Oct 25.

Abstract

It has long been clear that electron correlation methods exhibit unphysical compute scalings with molecular size, which has motivated the development of local correlation methods to discard effectively zero contributions in a controlled way to yield an approximate correlation energy. The ideal local correlation method should have a single numerical threshold that controls the dropping of terms with the ability to have that threshold set small enough so that the correlation energy is reproduced to enough significant figures such that the result is chemically identical. This work reports such a method for the second-order Møller-Plesset (MP2) theory. The theory, implementation, and testing of this local MP2 theory are reported. Thresholds ranging from 10-5 to 10-8 and basis sets ranging from split valence plus polarization through to quadruple-ζ are assessed for local MP2 calculations on a range of molecules, including linear chains and molecules with two- and three-dimensional character. The implementation is shared memory parallel via OpenMP and yields roughly 50% parallel efficiency with 16 cores for a large job. Considerable efforts were made to minimize memory demands, which increased as thresholds were tightened. A variety of relative energy calculations are presented as a function of threshold to provide some guidance to users on how to obtain adequate precision at a low compute cost. It is particularly clear that derivative properties require tighter thresholds in order to achieve an adequate precision.