On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation

TL;DR

This paper explores an exact formulation of multi-configuration density-functional theory, combining configuration interaction with orbital occupation functionals, leading to new theoretical frameworks like SOET and CASSOFT for correlated electron systems.

Contribution

It introduces a formal separation of correlation effects in orbital space and develops exact theoretical models such as SOET and CASSOFT, expanding the foundations of multi-configuration DFT.

Findings

Derived an adiabatic connection expression for the bath functional

Compared SOET with Density Matrix Embedding Theory (DMET)

Applied SOET to the Hubbard model and quantum chemical Hamiltonians

Abstract

The exact formulation of multi-configuration density-functional theory (DFT) is discussed in this work. As an alternative to range-separated methods, where electron correlation effects are split in the coordinate space, the combination of Configuration Interaction methods with orbital occupation functionals is explored at the formal level through the separation of correlation effects in the orbital space. When applied to model Hamiltonians, this approach leads to an exact Site-Occupation Embedding Theory (SOET). An adiabatic connection expression is derived for the complementary bath functional and a comparison with Density Matrix Embedding Theory (DMET) is made. Illustrative results are given for the simple two-site Hubbard model. SOET is then applied to a quantum chemical Hamiltonian, thus leading to an exact Complete Active Space Site-Occupation Functional Theory (CASSOFT) where active electrons are correlated explicitly within the CAS and the remaining contributions to the correlation energy are described with an orbital occupation functional. The computational implementation of SOET and CASSOFT as well as the development of approximate functionals are left for future work.