2023 Spring Graduate Colloquium Series: Anjy-Joe Olatunbosun
Density Functional Theory Transformed into a One-Electron-Reduced-Density-Matrix for the Capture of Static Correlation
Daniel Gibney Jan-Niklas Boyn, and David A. Mazziotti
Density Functional Theory (DFT), the most widely adopted method in modern computational chemistry, fails to describe accurately the electronic structure of strongly correlated systems. Here we show that DFT can be formally and practically transformed into a one-electron reduced-density-matrix (1-RDM) functional theory, which can address the limitations of DFT while retaining favorable computational scaling compared to wavefunction-based approaches. In addition to relaxing the idempotency restriction on the 1-RDM in the kinetic energy term, we add a quadratic 1-RDM-based term to DFTâ€™s density-based exchange correlation functional. Our approach, which we implement by quadratic semidefinite programming at DFTâ€™s computational scaling of O(r3), yields substantial improvements over traditional DFT in the description of static correlation in chemical structures and processes such as singlet biradicals and bond dissociations.