The energetics of the spin states of transition metal complexes have been explored with a variety of electronic structure methods, but the calculations require a compromise between accuracy and affordability. In this work, the spin splittings of several iron complexes are studied with multiconfiguration pair-density functional theory (MC-PDFT). The results are compared to previously published results obtained by complete active space second-order perturbation theory (CASPT2) and CASPT2 with coupled-cluster semicore correlation (CASPT2/CC). In contrast to CASPT2's systematic overstabilization of high-spin states with respect to the CASPT2/CC reference, MC-PDFT with the tPBE on-top functional understabilizes high-spin states. This systematic understabilization is largely corrected by revising the exchange and correlation contributions to the on-top functional using the high local-exchange approximation (tPBE-HLE). Moreover, tPBE-HLE correctly predicts the spin of the ground state in most cases, while CASPT2 incorrectly predicts high-spin ground states in all cases. This is encouraging for practical work because tPBE and tPBE-HLE are faster than CASPT2 by a factor of 50 even in a moderately sized example.
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