Bootstrap embedding with an unrestricted mean-field bath

A suite of quantum embedding methods have recently been developed where the Schmidt decomposition is applied to the full system wavefunction to derive basis states that preserve the entanglement between the fragment and the bath. The quality of these methods can depend heavily on the quality of the initial full system wavefunction. Most of these methods, including bootstrap embedding (BE) [M. Welborn et al; J. Chem. Phys. 145, 074102 (2016)], start from a spin-restricted mean-field wavefunction [call this restricted BE (RBE)]. Given that spin-unrestricted wavefunctions can capture a significant amount of strong correlation at the mean-field level, we suspect that starting from a spin-unrestricted mean-field wavefunction will improve these embedding methods for strongly correlated systems. In this work, BE is generalized to an unrestricted Hartree–Fock bath [call this unrestricted BE (UBE)], and UBE is applied to model hydrogen ring systems. UBE’s improved versatility over RBE is utilized to calculate high spin symmetry states that were previously unattainable with RBE. Ionization potentials, electron affinities, and spin-splittings are computed using UBE with accuracy on par with spin-unrestricted coupled cluster singles and doubles. Even for cases where RBE is viable, UBE converges more reliably. We discuss the limitations or weaknesses of each calculation and how improvements to RBE and density matrix embedding theory these past few years can also improve UBE.