Accurate energies of transition metal atoms, ions, and monoxides using selected configuration interaction and density-based basis-set corrections

The semistochastic heat-bath configuration interaction method is a selected configuration interaction plus perturbation theory method that has provided near-full configuration interaction (FCI) levels of accuracy for many systems with both single- and multi-reference character. However, obtaining accurate energies in the complete basis-set limit is hindered by the slow convergence of the FCI energy with respect to basis size. Here, we show that the recently developed basis-set correction method based on range-separated density functional theory can be used to significantly speed up basis-set convergence in SHCI calculations. In particular, we study two such schemes that differ in the functional used and apply them to transition metal atoms and monoxides to obtain total, ionization, and dissociation energies well converged to the complete-basis-set limit within chemical accuracy. Published under an exclusive license by AIP Publishing.

Automated summary

The semistochastic heat-bath configuration interaction method provides near-full configuration interaction accuracy but faces difficulties in basis size convergence. A basis-set correction method based on range-separated density functional theory has been shown to significantly speed up basis-set convergence in SHCI calculations.