Benchmarks and reliable DFT results for spin-crossover complexes

Abstract

DFT is used throughout nanoscience, especially when modeling spin-dependent properties that are important in spintronics. But standard quantum chemical methods (both CCSD(T) and self-consistent semilocal density functional calculations) fail badly for the spin adiabatic energy difference in Fe(II) spin-crossover complexes. We show that all-electron fixed-node diffusion Monte Carlo can be converged at significant computational cost, and that the B3LYP single-determinant has sufficiently accurate nodes, providing benchmarks for these systems. We also find that density-corrected DFT, using Hartree-Fock densities (HF-DFT), greatly improves accuracy and reduces dependence on approximations for these calculations. The small gap in the self-consistent DFT calculations for the high-spin state is consistent with this. For the spin adiabatic energy differences in these complexes, HF-DFT is both accurate and reliable, and we make a strong prediction for the Fe-Porphyrin complex. The "parameter-dilemma" of needing different amounts of mixing for different properties is eliminated by HF-DFT.