Incorporating a two-electron density functional into the two-electron density matrix cumulant

Josh Hollett, Gurleen Cheema, Ernesto Cruz Velázquez, and Caio Correia

The University of Winnipeg

An accurate model of electronic structure, within the framework of cumulant functional theory, that combines density matrix functional theory and a two-electron density functional is proposed. The approximate parameterization of the two-electron density matrix (2-RDM) is designed to treat so-called potential dependent correlation. Whereas, the two-electron density functional (TDF) is designed to capture the short-range component of so-called universal correlation. Parameterization of the 2-RDM involves including the leading-order terms that contribute to inter and intra-pair correlation while satisfying constraints of \(N\)-representability. A TDF allows for the precise accounting of all energetic consequences of any proposed electron-electron interaction ansatz ({\it i.e.}~kinetic, electron-electron potential and nucleus-electron potential). The advantages and challenges of such approaches will be discussed as well as preliminary results for atoms and small molecules.

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