A Linear-Scaling Method for Noncovalent Interactions: An Efficient Combination of Absolutely Localized Molecular Orbitals and a Local Random Phase Approximation Approach

Abstract

A novel method for the accurate and efficient calculation of interaction energies in weakly bound complexes composed of a large number of molecules is presented. The new ALMO+RPAd method circumvents the prohibitive scaling of coupled cluster singles and doubles while still providing similar accuracy across a diverse range of weakly bound chemical systems. Linear-scaling procedures for the Fock build are given utilizing absolutely localized molecular orbitals (ALMOs), resulting in the a priori exclusion of basis set superposition errors. A bespoke data structure and algorithm using density fitting are described, leading to linear scaling for the storage and computation of the two-electron integrals. Electron correlation is included through a new, linear-scaling pairwise local random phase approximation approach, including exchange interactions, and decomposed into purely dispersive excitations (RPAxd). Collectively, these allow meaningful decomposition of the interaction energy into physically distinct contributions: electrostatic, polarization, charge transfer, and dispersion. Comparison with symmetry-adapted perturbation theory shows good qualitative agreement. Tests on various dimers and the S66 benchmark set demonstrate results within 0.5 kcal mol-1 of coupled cluster singles and doubles results. On a large cluster of water molecules, we achieve calculations involving over 3500 orbital and 12,000 auxiliary basis functions in under 10 min on a single CPU core.