Multi-state effective Hamiltonian and size-consistency corrections in stochastic configuration interactions

TL;DR

This paper advances stochastic configuration interaction methods by introducing a multi-state effective Hamiltonian approach with size-consistency corrections, enabling efficient and accurate calculation of electronic states in quantum chemistry.

Contribution

It presents a novel state-selective partitioning algorithm for MSQMC and develops size-consistency corrections to improve the initiator approximation accuracy.

Findings

The new algorithm reduces computational cost for multiple electronic states.

Size-consistency corrections significantly recover initiator errors.

Most initiator error stems from truncated CI nature, correctable by proposed methods.

Abstract

Model space quantum Monte Carlo (MSQMC) is an extension of full configuration interaction QMC (FCIQMC) that allows us to calculate quasi-degenerate and excited electronic states by sampling the effective Hamiltonian in the model space. We introduce a novel algorithm based on the state-selective partitioning for the effective Hamiltonian using left eigenvectors to calculate several electronic states simultaneously at much less computational cost than the original MSQMC with the energy dependent partitioning. The sampling of walkers in MSQMC is analyzed in the single reference limit using a stochastic algorithm for higher-order perturbation energies by the analogy of the deterministic case utilizing a full configuration interaction program. We further develop size-consistency corrections of the initiator adaptation (i-MSQMC) in three different ways, i.e. the coupled electron pair approximation, a posteriori, and second-order pertrubative corrections. It is clearly demonstrated that most of the initiator error is originating from the deficiency of proper scaling of correlation energy due to its truncated CI nature of the initiator approximation, and that the greater part of the error can be recovered by the size-consistency corrections developed in this work.