Magnetic exchange coupling in Cu dimers studied with modern multireference methods and broken-symmetry coupled cluster theory

Abstract

AbstractSpin-state energetics of exchange-coupled copper complexes pose a persistent challenge for applied quantum chemistry. Here, we provide a comprehensive comparison of all available theoretical approaches to the problem of exchange coupling in two antiferromagnetically coupled bis-μ-hydroxo Cu(II) dimers. The evaluated methods include multireference methods based on the density matrix renormalization group (DMRG), multireference methods that incorporate dynamic electron correlation either perturbatively, such as the N-electron valence state perturbation theory, or variationally, such as the difference-dedicated configuration interaction. In addition, we contrast the multireference results with those obtained using broken-symmetry approaches that utilize either density functional theory or, as demonstrated here for the first time in such systems, a local implementation of coupled cluster theory. The results show that the spin-state energetics of these copper dimers are dominated by dynamic electron correlation and represent an impossible challenge for multireference methods that rely on brute-force expansion of the active space to recover correlation energy. Therefore, DMRG-based methods even at the limit of their applicability cannot describe quantitatively the antiferromagnetic exchange coupling in these dimers, in contrast to dinuclear complexes of earlier transition metal ions. The convergence of the broken-symmetry coupled cluster approach is studied and shown to be a limiting factor for the practical application of the method. The advantages and disadvantages of all approaches are discussed, and recommendations are made for future developments.