Configuration interaction based on constrained density functional theory: A multireference method

Existing density functional theory (DFT) methods are typically very effective in capturing dynamic correlation, but run into difficulty treating near-degenerate systems where static correlation becomes important. In this work, we propose a configuration interaction (CI) method that allows one to use a multireference approach to treat static correlation but incorporates DFT’s efficacy for the dynamic part as well. The new technique uses localized charge or spin states built by a constrained DFT approach to construct an active space in which the effective Hamiltonian matrix is built. These local configurations have significantly less static correlation compared to their delocalized counterparts and possess an essentially constant amount of self-interaction error. Thus their energies can be reliably calculated by DFT with existing functionals. Using a small number of local configurations as different references in the active space, a simple CI step is then able to recover the static correlation missing from the localized states. Practical issues of choosing configurations and adjusting constraint values are discussed, employing as examples the ground state dissociation curves of $H2+$⁠, $H2$⁠, and LiF. Excellent results are obtained for these curves at all interatomic distances, which is a strong indication that this method can be used to accurately describe bond breaking and forming processes.