Static embedding with pair coupled cluster doubles based methods

Abstract

Quantum embedding methods have recently been significantly developed to model large molecular structures. This work proposes a novel wave function theory in a density functional theory (WTF-in-DFT) embedding scheme based on pair-coupled cluster doubles (pCCD)-type methods. While pCCD can reliably describe strongly-correlated systems with mean-field-like computational cost, the large extent of the dynamic correlation can be accounted for by (linearized) coupled-cluster corrections on top of the pCCD wave function. Here we focus on the linearized coupled-cluster singles and doubles (LCCSD) ansatz for electronic ground states and its extension to excited states within the equation of motion (EOM) formalism. We test our EOM-pCCD-LCCSD-in-DFT approach for the vertical excitation energies of the hydrogen-bonded water–ammonia complex, micro-solvated thymine, and uranyl tetrahalides (UO₂X₄²⁻, X = F, Cl, Br). Furthermore, we assess the quality of the embedding potential using an orbital entanglement and correlation analysis. The approximate embedding models successfully capture changes in the excitation energies going from bare fragments to supramolecular structures and represent a promising computational method for excited states in large molecular systems.