Reimagining the Wave Function in Density Functional Theory: Exploring Strongly Correlated States in Pancake-Bonded Radical Dimers

Abstract

Pancake bonding between π-conjugated radicals challenges conventional electronic structure approximations, due to the presence of both dispersion (van der Waals) interactions and "strong" electron correlation. Here we use a reimagined wave function-in-density functional theory (DFT) approach to model pancake bonds. Our generalized self-interaction correction extends DFT's reference system of noninteracting electrons, by introducing electron-electron interactions within an active space. We show that a small variation on our previous derivation recovers a DFT-corrected complete active space method proposed by Pijeau and Hohenstein. Comparison of the two approaches shows that the latter provides reasonable dissociation curves for single bonds and pancake bonds, including excited states inaccessible to conventional linear response time-dependent DFT. The results motivate broader adoption of wavefunction-in-DFT approaches for modeling pancake bonds.