Localized active space pair-density functional theory

Pandharkar, R.; Hermes, M. R.; Cramer, C. J.; Truhlar, D. G.; Gagliardi, L.
J. Chem. Theor. Comput. 2021, 17, 2843 (doi:10.1021/acs.jctc.1c00067).

Accurate quantum chemical methods for the prediction of spin-state energy gaps for strongly correlated systems are computationally expensive and scale poorly with the size of the system. This makes calculations for many experimentally interesting molecules impractical even with abundant computational resources. In previous work, we have shown that the localized active space (LAS) self-consistent field (SCF) method is an efficient way to obtain multi-configuration SCF wave functions of comparable quality to the corresponding complete active space (CAS) ones. To obtain quantitative results, a post-SCF method is needed to estimate the complete correlation energy. One such method is multiconfiguration pair-density functional theory (PDFT), which calculates the energy based on the density and on-top pair density obtained from a multiconfiguration wave function. In this work we introduce localized-active-space pair-density functional theory, which uses a LAS wave function for subsequent PDFT calculations. The method is tested by computing spin-state energies and gaps in conjugated organic molecules and bimetallic compounds and comparing to the corresponding CAS-PDFT values.