Diffusion Monte Carlo Perspective on the Spin-State Energetics of [Fe(NCH)6]2+

The energy difference between the high spin and the low spin state of the model compound [Fe­(NCH)6]2+ is investigated by means of Diffusion Monte Carlo (DMC), where special attention is dedicated to analyzing the effect of the fix node approximation on the accuracy of the results. For this purpose, we compare several Slater–Jastrow and multireference Slater–Jastrow trial wave functions. We found that a Slater–Jastrow trial wave function constructed with the generalized Kohn–Sham orbitals from hybrid DFT represents the optimal choice. This is understood by observing that hybrid functionals account for the subtle balance between exchange and correlation effects and the respective orbitals accurately describe the ligand–metal hybridization as well as the charge reorganization accompanying the spin transition. Finally the DMC results are compared with those obtained by Hartree–Fock, DFT, CASSCF, and CASPT2. While there is no clear reference value for the high spin–low spin energy difference, DMC and high level CCSD­(T) calculations agree within around 0.3 eV.