Many-Body Basis Set Amelioration Method for Incremental Full Configuration Interaction

TL;DR

The paper introduces MBBSA, a method that enhances incremental full configuration interaction (iFCI) to handle larger basis sets efficiently, achieving significant cost reductions while maintaining chemical accuracy.

Contribution

MBBSA is a novel approach that approximates high-accuracy iFCI results using inexpensive calculations, enabling larger system studies with substantial computational savings.

Findings

MBBSA achieves 60-92% cost savings over standard iFCI.

MBBSA maintains chemical accuracy in total and relative energies.

Practical utility demonstrated on complex chemical reactions.

Abstract

Incremental full configuration interaction (iFCI) is polynomial-cost approach to the FCI limit of electronic structure. This article introduces the many-body basis set amelioration (MBBSA) method, which is designed to allow iFCI to be applicable to larger atomic orbital basis sets. MBBSA uses a series of inexpensive iFCI calculations to approximate the correlation energy that would be found using a more expensive, highly accurate iFCI calculation. When compared to standard iFCI computations on smaller molecules in triple-zeta and larger basis sets, MBBSA provides approximations to total and relative energies within chemical accuracy. MBBSA yields cost savings of between 60 and 92% when compared to standard iFCI calculations, with larger systems having increased savings. Tests of MBBSA on two reactions that involve highly correlated systems, the automerization of cyclobutadiene and a Criegee intermediate reaction, show that MBBSA has practical utility for studying realistic chemistries.