The Use of Effective Core Potentials with Multiconfiguration Pair-Density Functional Theory

Abstract

The reliable and accurate prediction of chemical properties is a key goal in quantum chemistry. Transition-metal-containing complexes can often pose difficulties to quantum mechanical methods for multiple reasons, including many electron configurations contributing to the overall electronic description of the system and the large number of electrons significantly increasing the amount of computational resources required. Often, multiconfigurational electronic structure methods are employed for such systems, and the cost of these calculations can be reduced by the use of an effective core potential (ECP). In this work, we explore both theoretical considerations and performances of ECPs applied in the context of multiconfiguration pair-density functional theory (MC-PDFT). A mixed-basis set approach is used, using ECP basis sets for transition metals and all-electron basis sets for nonmetal atoms. We illustrate the effects that an ECP has on the key parameters used in the computation of MC-PDFT energies, and we explore how ECPs affect the prediction of physical observables for chemical systems. The dissociation curve for a metal dimer was explored, and ionization energies for transition metal-containing diatomic systems were computed and compared to experimental values. In general, we find that ECP approaches employed with MC-PDFT are able to predict ionization energies with improved accuracy compared to traditional Kohn–Sham density functional theory approaches.