Generalized Many-Body Expanded Full Configuration Interaction Theory

TL;DR

This paper extends the MBE-FCI method to handle complex molecular systems with both weak and strong electron correlation, achieving near-exact results for large and diverse systems.

Contribution

It introduces a generalized MBE-FCI approach that uses minimal or empty reference spaces, enabling unbiased, near-exact correlation energy calculations for complex molecules.

Findings

Accurately computed energies for the Hubbard model, chromium dimer, and benzene.

Demonstrated the method's ability to handle large, strongly correlated systems.

Showed potential for near-exact results in complex chemical applications.

Abstract

Facilitated by a rigorous partitioning of a molecular system's orbital basis into two fundamental subspaces - a reference and an expansion space, both with orbitals of unspecified occupancy - we generalize our recently introduced many-body expanded full configuration interaction (MBE-FCI) method to allow for electron-rich model and molecular systems dominated by both weak and strong correlation to be addressed. By employing minimal or even empty reference spaces, we show through calculations on the one-dimensional Hubbard model with up to 46 lattice sites, the chromium dimer, and the benzene molecule how near-exact results may be obtained in a entirely unbiased manner for chemical and physical problems of not only academic, but also applied chemical interest. Given the massive parallelism and overall accuracy of the resulting method, we argue that generalized MBE-FCI theory possesses an immense potential to yield near-exact correlation energies for molecular systems of unprecedented size, composition, and complexity in the years to come.