Improving Predictions of Spin-Crossover Complex Properties through DFT Calculations with a Local Hybrid Functional

Abstract

We conducted a study on the performance of the local hybrid exchange–correlation functional PBE0r for a set of 95 experimentally characterized iron spin-crossover (SCO) complexes [Vennelakanti, V.; J. Chem. Phys. 2023, 159, 024120]. The PBE0r functional is a variant of PBE0 where the exchange correction is restricted to on-site terms formulated on the basis of local orbitals. We determine the free parameters of the PBE0r functional against the experimental data and other hybrid functionals. With a Hartree–Fock (HF) exchange factor of 4%, the PBE0r functional accurately reproduces the electronic and free-energy trends predicted in prior DFT studies for these 95 complexes by using the B3LYP functional. Larger values of HF exchange stabilize high-spin states. The PBE0r-predicted bond lengths tend to exceed the experimental bond lengths, although bond lengths are less sensitive to HF exchange than in global hybrids. The predicted SCO transition temperatures T_1/2 from PBE0r correlate moderately with the experimental transition temperatures, showing a slight improvement compared to the previous modB3LYP-predicted T_1/2. This study suggests that the PBE0r functional is computationally cost-effective and offers the possibility of simulating larger complexes with accuracy comparable to global hybrid functionals, provided the HF-exchange parameter is carefully optimized.