Reaching Full Correlation through Nonorthogonal Configuration Interaction: A Second-Order Perturbative Approach (2005.03962v2)

Abstract: Nonorthogonal multireference methods can predict statically correlated adiabatic energies while providing chemical insight through the combination of diabatic reference states. However, reaching quantitative accuracy using nonorthogonal multireference expansions remains a significant challenge. In this work, we present the first rigorous perturbative correction to nonorthogonal configuration interaction, allowing the remaining dynamic correlation to be reliably computed. Our second-order "NOCI-PT2" theory exploits a zeroth-order generalised Fock Hamiltonian and builds the first-order interacting space using single and double excitations from each reference determinant. This approach therefore defines the rigorous nonorthogonal extension to conventional multireference perturbation theory. We find that NOCI-PT2 can quantitatively predict multireference potential energy surfaces and provides state-specific ground and excited states for adiabatic avoided crossings. Furthermore, we introduce an explicit imaginary-shift formalism requiring shift values that are an order of magnitude smaller than those used in conventional multireference perturbation theory.