Selected configuration interaction dressed by perturbation

TL;DR

This paper introduces advanced selected configuration interaction methods with perturbative corrections that efficiently approximate full CI energies, including a multi-state approach that reduces storage bottlenecks.

Contribution

It develops both state-specific and multi-state sCI methods based on CIPSI, incorporating an effective Hamiltonian with a low-rank factorization to improve efficiency.

Findings

Achieves near FCI accuracy with fewer determinants.

Removes storage bottleneck via low-rank factorization.

Provides a new multi-state sCI algorithm.

Abstract

Selected configuration interaction (sCI) methods including second-order perturbative corrections provide near full CI (FCI) quality energies with only a small fraction of the determinants of the FCI space. Here, we introduce both a state-specific and a multi-state sCI method based on the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm. The present method revises the reference (internal) space under the effect of its interaction with the outer space via the construction of an effective Hamiltonian, following the shifted-Bk philosophy of Davidson and coworkers. In particular, the multi-state algorithm removes the storage bottleneck of the effective Hamiltonian via a low-rank factorization of the dressing matrix.