Cluster Amplitudes and Their Interplay with Self-Consistency in Density Functional Methods.

The front cover artwork is provided by the Mosquera group at Montana State University, Bozeman. The image shows theoretical elements involved in the density-functional calculations that are free of spurious fractional charges. Read the full text of the Research Article at 10.1002/cphc.202200592.

Cluster Amplitudes and Their Interplay with Self-Consistency in Density Functional Methods.

Density functional theory (DFT) provides convenient electronic structure methods for the study of molecular systems and materials. Regular Kohn-Sham DFT calculations rely on unitary transformations to determine the ground-state electronic density, ground state energy, and related properties. However, for dissociation of molecular systems into open-shell fragments, due to the self-interaction error present in a large number of density functional approximations, the self-consistent procedure based on the this type of transformation gives rise to the well-known charge delocalization problem. To avoid this issue, we showed previously that the cluster operator of coupled-cluster theory can be utilized within the context of DFT to solve in an alternative and approximate fashion the ground-state self-consistent problem. This work further examines the application of the singles cluster operator to molecular ground state calculations. Two approximations are derived and explored: i) A linearized scheme of the quadratic equation used to determine the cluster amplitudes. ii) The effect of carrying the calculations in a non-self-consistent field fashion. These approaches are found to be capable of improving the energy and density of the system and are quite stable in either case. The theoretical framework discussed in this work could be used to describe, with an added flexibility, quantum systems that display challenging features and require expanded theoretical methods.