Multiconfigurational Correlation at DFT + U Cost: On-Site Electron-Electron Interactions Yield a Block-Localized Configuration Interaction Hamiltonian.

This work presents a first-principles wavefunction-in-DFT approach based on the Hubbard density functional theory (DFT) + U method. This approach begins with the standard DFT reference system of noninteracting electrons and introduces an electron-electron interaction projected onto DFT+ U -type atomic states. The reference system's configuration interaction Hamiltonian is block-localized to these states and can be expressed in terms of state occupation numbers, state self-energies (which correspond to unscreened Hubbard U values), and the promotion energies of doubly excited Slater determinants. Simple approximations for the promotion energies provide multiconfigurational correlation energies without requiring explicit orbital localization/transform. Numerical results for fractionally occupied chromium atom, bonded chromium dimer, dissociating covalent bonds, and large active spaces show that the approach provides beyond-zero-sum accuracy at computational cost comparable to standard DFT+ U .