Approximations of density matrices in N-electron valence state second-order perturbation theory (NEVPT2). I. Revisiting the NEVPT2 construction.

Abstract

Over the last decade, the second-order N-electron valence state perturbation theory (NEVPT2) has developed into a widely used multireference perturbation method. To apply NEVPT2 to systems with large active spaces, the computational bottleneck is the construction of the fourth-order reduced density matrix. Both its generation and storage become quickly problematic beyond the usual maximum active space of about 15 active orbitals. To reduce the computational cost of handling fourth-order density matrices, the cumulant approximation (CU) has been proposed in several studies. A more conventional strategy to address the higher-order density matrices is the pre-screening approximation (PS), which is the default one in the ORCA program package since 2010. In the present work, the performance of the CU, PS, and extended PS (EPS) approximations for the fourth-order density matrices is compared. Following a pedagogical introduction to NEVPT2, contraction schemes, as well as the approximations to density matrices, and the intruder state problem are discussed. The CU approximation, while potentially leading to large computational savings, virtually always leads to intruder states. With the PS approximation, the computational savings are more modest. However, in conjunction with conservative cutoffs, it produces stable results. The EPS approximation to the fourth-order density matrices can reproduce very accurate NEVPT2 results without any intruder states. However, its computational cost is not much lower than that of the canonical algorithm. Moreover, we found that a good indicator of intrude states problems in any approximation to high order density matrices is the eigenspectra of the Koopmans matrices.