Reaching Full Correlation through Nonorthogonal Configuration Interaction: A Second-Order Perturbative Approach

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.

Accepted manuscript in the Journal of Chemical Theory and Computation. [16 pages, 5 figures]

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• Nambu-Covariant Many-Body Theory I: Perturbative Approximations
• Self-consistent Møller-Plesset Perturbation Theory For Excited States
• Precise Quantum Chemistry calculations with few Slater Determinants
• Natural Excitation Framework for Defining the External Space: Uncontracted and Internally Contracted Multireference Nonorthogonal Wavefunction Theories