LiF has an avoided crossing between an ionic state and a covalent state and is widely used to test electronic structure methods. Prior studies have shown that CMS-PDFT gives similar potential curves to XMS-CASPT2, whereas MC-and HMC-PDFT display unphysical state crossings between 4 and 6 Å as well as a large dip in the potential curve for both states (Figure ). As can be seen in Figure , L-PDFT and HL-PDFT give the correct potential curve shape as well as the correct state ordering in this region, and neither method has the large dip in the potential curve at 4 Å.