R2022: A DFT/MRCI Ansatz with Improved Performance for Double Excitations.

A reformulation of the combined density functional theory and multireference configuration interaction method (DFT/MRCI) is presented. Expressions for ab initio matrix elements are used to derive correction terms for a new effective Hamiltonian. On the example of diatomic carbon, the correction terms are derived, focusing on the doubly excited 1 Δ g state, which was problematic in previous formulations of the method, as were double excitations in general. The derivation shows that a splitting of the parameters for intra- and interorbital interactions is necessary for a concise description of the underlying physics. Results for 1 L a and 1 L b states in polyacenes and 1 A u and 1 A g states in mini-β-carotenoids suggest that the presented formulation is superior to former effective Hamiltonians. Furthermore, statistical analysis reveals that all the benefits of the previous DFT/MRCI Hamiltonians are retained. Consequently, the here presented formulation should be considered as the new standard for DFT/MRCI calculations.