SparseMaps—A systematic infrastructure for reduced-scaling electronic structure methods. VI. Linear-scaling explicitly correlated N-electron valence state perturbation theory with pair natural orbital

摘要

In this work, a linear scaling explicitly correlated N-electron valence state perturbation theory (NEVPT2-F12) is presented. By using the idea of a domain-based local pair natural orbital (DLPNO), computational scaling of the conventional NEVPT2-F12 is reduced to near-linear scaling. For low-lying excited states of organic molecules, the excitation energies predicted by DLPNO-NEVPT2-F12 are as accurate as the exact NEVPT2-F12 results. Some cluster models of rhodopsin are studied using the new algorithm. Our new method is able to study systems with more than 3300 basis functions and an active space containing 12 π-electrons and 12 π-orbitals. However, even larger calculations or active spaces would still be feasible.