Coherent heat-bath configuration interaction with many-body perturbation theory for multivalent atoms

Abstract

Combinatorial growth of configuration-interaction spaces limits accurate calculations as the valence-electron number and orbital space increase. To reduce the size of the configuration-interaction space, we develop coherent heat-bath configuration interaction in a configuration-state-function basis and combine it with many-body perturbation theory. Configurations are selected by thresholding their coherent couplings to target wave functions, and a perturbative correction recovers residual valence correlation. For Al, a stringent threshold gives about 16-37 fold compression with excitation-energy deviations from the uncompressed calculations below 0.74 /cm; a looser threshold gives 63-113 fold compression with a maximum deviation of 18.22 /cm. For Si and P, roughly threefold to eightfold compression is achieved with maximum relative deviations of approximately 0.70% and 0.32%, respectively, for optical excitation energies. The perturbative correction improves the accuracy of all calculated total energies. These results support extending the method to high-precision calculations in more complex atomic systems.