Even-handed subsystem selection in projection-based embedding

TL;DR

This paper introduces an even-handed orbital partitioning method for projection-based embedding that maintains consistency across geometries, improving accuracy in complex chemical systems.

Contribution

The paper presents a novel even-handed framework for localized orbital partitioning that ensures consistent subsystems during large geometry changes in projection-based embedding.

Findings

Enables chemically accurate embedding with modestly-sized regions.

Addresses issues of unphysical cusps and discontinuities in potential energy surfaces.

Proven effective in reactions and catalytic systems.

Abstract

Projection-based embedding offers a simple framework for embedding correlated wavefunction methods in density functional theory. Partitioning between the correlated wavefunction and density functional subsystems is performed in the space of localized molecular orbitals. However, during a large geometry change--such as a chemical reaction--the nature of these localized molecular orbitals, as well as their partitioning into the two subsystems, can change dramatically. This can lead to unphysical cusps and even discontinuities in the potential energy surface. In this work, we present an even-handed framework for localized orbital partitioning that ensures consistent subsystems across a set of molecular geometries. We illustrate this problem and the even-handed solution with a simple example of an SN2 reaction. Applications to a nitrogen umbrella flip in a cobalt-based CO2 reduction catalyst and to the binding of CO to Cu clusters are presented. In both cases, we find that even-handed partitioning enables chemically accurate embedding with modestly-sized embedded regions for systems in which previous partitioning strategies are problematic.