Multiconfiguration pair-density functional theory (MC-PDFT) is a computational method that utilizes multiconfigurational wave functions and a special type of density functional theory (DFT) to produce a model that can accurately and efficiently simulate the electronic structures of systems which a single configuration state cannot reasonably predict. Effective core potentials (ECP) are potential energy functions that are used to model nonbonding core electrons at a lower computational cost by excluding the core electrons from the active space and allowing more computational power to devote to the electrons of interest. In this study, ECPs were used in conjunction with MC-PDFT to study the effectiveness of the Stuttgart RSC 1997 ECP and LANL2DZ ECP basis sets using the tPBE<sup> </sup>and ftPBE functionals on several 3d transition metal systems, of which included singular metal atoms, metal dimers, and diatomic molecules containing at least one metal atom. To test the effectiveness of these basis sets, several metrics were explored, including ionization energy calculations, bond dissociation energy calculations, and geometry optimizations, where the results were compared to experimental literature values and values calculated using non-ECP basis sets. The results of this study, including the effectiveness of the ECP’s used, provide valuable insight into the use of ECPs in conjunction with MC-PDFT and will be useful in the future studies of metal-electrode-based single molecule electronic devices.

Accuracy of multiconfiguration pair-density functional theory with effective core potentials: Application to 3d transition metal systems

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