A shortcut to the thermodynamic limit for quantum many-body calculations of metals

Computationally efficient and accurate quantum mechanical approximations to solve the many-electron Schrödinger equation are crucial for computational materials science. Methods such as coupled cluster theory show potential for widespread adoption if computational cost bottlenecks can be removed. For example, extremely dense k-point grids are required to model long-range electronic correlation effects, particularly for metals. Although these grids can be made more effective by averaging calculations over an offset (or twist angle), the resultant cost in time for coupled cluster theory is prohibitive. We show here that a single special twist angle can be found using the transition structure factor, which provides the same benefit as twist averaging with one or two orders of magnitude reduction in computational time. We demonstrate that this not only works for metal systems but also is applicable to a broader range of materials, including insulators and semiconductors.

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.