Parquet theory for molecular systems: Formalism and static kernel parquet approximation

Abstract

The GW approximation has become a method of choice for predicting quasiparticle properties in solids and large molecular systems, owing to its favorable accuracy–cost balance. However, its accuracy is the result of a fortuitous cancellation of vertex corrections in the polarizability and self-energy. Hence, when attempting to go beyond GW through the inclusion of vertex corrections, the accuracy can deteriorate if this delicate balance is disrupted. In this work, we explore an alternative route that theoretically goes beyond GW: the parquet formalism. Unlike approaches that focus on a single correlation channel, such as the electron–hole channel in GW or the particle–particle channel in T-matrix theory, parquet theory treats all two-body scattering channels on an equal footing. We present the formal structure of the parquet equations, which couple the one-body Green’s function, the self-energy, and the two-body vertex. We discuss the approximations necessary to solve this set of equations, the advantages and limitations of this approach, outline its implementation for molecular systems, and assess its accuracy for principal ionization potentials of small molecular systems.