Ab Initio Approach for Quantum Magnets with Coupled Cluster and Transcorrelation

The nearest-neighbour exchange coupling J 1 is the simplest ingredient of model Hamiltonians used to understand magnetism in real materials. Nevertheless, its ab initio determination requires a high-level correlation treatment and a large basis for wave function expansion. Here we compute J 1 for five oxygen-bridged spin-1/2 quantum magnets --- Sr 2 CuO 3, La 2 CuO 4, NdNiO 2, ZnCu 3 (OH) 6 Cl 2, and Li 2 CuO 2 --- spanning bridging angles from 180 to 94 and the crossover from antiferromagnetic to ferromagnetic coupling, using embedded-cluster methodology. To describe the open-shell singlets we use 2-determinant coupled cluster with single and double excitations, which recovers the orbital-breathing enhancement of superexchange from a minimal reference. Basis-set errors are found to be large: extrapolation to the complete basis-set (CBS) limit shifts J 1 by up to 50 meV from bases of double- ζ quality. Transcorrelated Hamiltonians reproduce the CBS estimates with modest basis set sizes, yielding an excellent accuracy against experiment at highly affordable cost. These results are the first application of transcorrelated methods in strongly correlated solid-state systems, and establish transcorrelation as a powerful theory in computational research of materials.