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

Spin-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.

The Ranked-Orbital Approach to Selecting Active Spaces

The past decade has seen a great increase in the application of high-throughput computation to a variety of important problems in chemistry. However, one area which has been resistant to the high-throughput approach is multireference wave function methods, in large part due to the technicalities of setting up these calculations and in particular the not always intuitive challenge of active space selection. As we look towards a future of applying high-throughput computation to all areas of chemistry, it is important to prepare these methods for large-scale automation. Here, we propose a ranked-orbital approach to selecting active spaces with the goal of standardizing multireference methods for high-throughput computation. This method allows for the meaningful comparison of different active space selection schemes and orbital localizations, and we demonstrate the utility of this approach across 1120 multireference calculations for the excitation energies of small molecules. Additionally, we propose our own active space selection scheme that estimates the importance of an orbital for the active space through a pair-interaction framework from orbital energies and features of the Hartree-Fock exchange matrix. We call this new scheme the "Approximate Pair Coefficient" (APC) method and it performs quite well for the test systems presented

The Ranked-Orbital Approach to Selecting Active Spaces

The past decade has seen a great increase in the application of high-throughput computation to a variety of important problems in chemistry. However, one area which has been resistant to the high-throughput approach is multireference wave function methods, in large part due to the technicalities of setting up these calculations and in particular the not always intuitive challenge of active space selection. As we look towards a future of applying high-throughput computation to all areas of chemistry, it is important to prepare these methods for large-scale automation. Here, we propose a ranked-orbital approach to selecting active spaces with the goal of standardizing multireference methods for high-throughput computation. This method allows for the meaningful comparison of different active space selection schemes and orbital localizations, and we demonstrate the utility of this approach across 1120 multireference calculations for the excitation energies of small molecules. Additionally, we propose our own active space selection scheme that estimates the importance of an orbital for the active space through a pair-interaction framework from orbital energies and features of the Hartree-Fock exchange matrix. We call this new scheme the "Approximate Pair Coefficient" (APC) method and it performs quite well for the test systems presented

Spontaneous bond dissociation cascades induced by Ben clusters (n = 2,4)

Be4 clusters are very powerful Lewis acids leading to the total dissociation of all the bonds of the Lewis bases interacting with them. The product of the bond dissociation cascade possesses a hyper-coordinated center. Multireference methods are needed to correctly describe these complexes.

Modern multireference methods and their application in transition metal chemistry

Transition metal chemistry is a challenging playground for quantum chemical methods owing to the simultaneous presence of static and dynamic electron correlation effects in many systems. Wavefunction based multireference (MR)...

Multireference Theories of Electron Correlation Based on the Driven Similarity Renormalization Group

The driven similarity renormalization group (DSRG) provides an alternative way to address the intruder state problem in quantum chemistry. In this review, we discuss recent developments of multireference methods based on the DSRG. We provide a pedagogical introduction to the DSRG and its various extensions and discuss its formal properties in great detail. In addition, we report several illustrative applications of the DSRG to molecular systems.