Quantum embedding for molecules using auxiliary particles – the ghost Gutzwiller Ansatz

Abstract

Strong/static electronic correlation mediates the emergence of remarkable phases of matter, and underlies the exceptional reactivity properties in transition metal-based catalysts. Modeling strongly correlated molecules and solids calls for multi-reference Ansätze, which explicitly capture the competition of energy scales characteristic of such systems. With the efficient computational screening of correlated solids in mind, the ghost Gutzwiller (gGut) Ansatz has been recently developed. This is a variational Ansatz which can be formulated as a self-consistent embedding approach, describing the system within a non-interacting, quasiparticle model, yet providing accurate spectra in both low and high energy regimes. Crucially, small fragments of the system are identified as responsible for the strong correlation, and are therefore enhanced by adding a set of auxiliary orbitals, the ghosts. These capture many-body correlations through one-body fluctuations and subsequent out-projection when computing physical observables. gGut has been shown to accurately describe multi-orbital lattice models at modest computational cost. In this work, we extend the gGut framework to strongly correlated molecules, for which it holds special promise. Indeed, despite the asymmetric embedding treatment, the quasiparticle Hamiltonian effectively describes all major sources of correlation in the molecule: strong correlation through the ghosts in the fragment, and dynamical correlation through the quasiparticle description of its environment. To adapt the gGut Ansatz for molecules, we address the fact that, unlike in the lattice model previously considered, electronic interactions in molecules are not local. Hence, we explore a hierarchy of approximations of increasing accuracy capturing interactions between fragments and environment, and within the environment, and discuss how these affect the embedding description of correlations in the whole molecule. We will compare the accuracy of the gGut model with established methods to capture strong correlation within active space formulations, and assess the realistic use of this novel approximation to the theoretical description of correlated molecular clusters.