We present an efficient implementation of the random phase approximation (RPA) for molecular systems within the domain-based local pair natural orbital (DLPNO) framework. With optimized parameters, DLPNO-RPA achieves approximately 99.9% accuracy in the total correlation energy compared to a canonical implementation, enabling highly accurate reaction energies and potential energy surfaces to be computed while substantially reducing computational costs. As an application, we demonstrate the capability of DLPNO-RPA to efficiently calculate basis set-converged binding energies for a set of large molecules, with results showing excellent agreement with high-level reference data from both coupled cluster and diffusion Monte Carlo. This development paves the way for the routine use of RPA-based methods in molecular quantum chemistry.
@article{arxiv.2411.07352,
title = {Efficient Implementation of the Random Phase Approximation with Domain-based Local Pair Natural Orbitals},
author = {Yu Hsuan Liang and Xing Zhang and Garnet Kin-Lic Chan and Timothy C. Berkelbach and Hong-Zhou Ye},
journal= {arXiv preprint arXiv:2411.07352},
year = {2025}
}