Ghost embedding bridging chemistry and one-body theories

Abstract

Phenomenological rules play a central role in the design of chemical reactions and materials with targeted properties. Typically, these are formulated heuristically in terms of non-interacting orbitals and bands yet show remarkable accuracy in predicting the complex behavior of intrinsically interacting many-body systems. While their non-interacting formulation makes them easy to interpret, it potentially hinders the development of new rules for systems governed by strong correlations, such as transition-metal-based materials. In this work, we present a rigorous framework that allows bridging between fully interacting, even strongly correlated, systems and an effective one-body picture in terms of quasiparticles. Furthermore, we present a computational strategy to efficiently and accurately access the main components of such a description: the embedding approximation of the ghost Gutzwiller ansatz. We illustrate the capabilities of this quasiparticle formulation on the Woodward–Hoffmann rules and apply their reformulated version to toy “reactions,” which exemplify the main scenarios covered by them.