Nonlocal rung-3.5 correlation from the density matrix expansion: Flat-plane condition, thermochemistry, and kinetics

The rung-3.5 approach to density functional theory constructs nonlocal approximate correlation from the expectation values of nonlocal one-electron operators. This offers an inexpensive solution to hybrid functionals' imbalance between exact nonlocal exchange and local approximate correlation. Our rung-3.5 correlation functionals also include a local complement to the nonlocal ingredient, analogous to the local exchange component of a hybrid functional. Here, we use the density matrix expansion (DME) to build rung-3.5 complements. We demonstrate how these provide a measure of local fractional occupancy and use them to approximate the flat-plane condition. We also use these complements in a three-parameter nonlocal correlation functional compatible with full nonlocal exchange. This functional approaches the accuracy of widely used hybrids for molecular thermochemistry and kinetics. The DME provides a foundation for practical, minimally empirical, nonlocal correlation functionals compatible with full nonlocal local exchange.