Understanding the mechanism stabilizing intermediate spin states in Fe(II)-Porphyrin (1712.07710v1)

Abstract: Spin fluctuations in Fe(II)-porphyrins are at the heart of heme-proteins functionality. Despite significant progress in porphyrin chemistry, the mechanisms that rule spin state stabilisation remain elusive. Here, it is demonstrated by using multiconfigurational quantum chemical approaches, including the novel Stochastic-CASSCF method, that electron delocalization between the metal centre and the pi system of the macrocycle differentially stabilises the triplet spin states over the quintet. This delocalisation takes place via charge-transfer excitations, involving the out-of-plane iron d orbitals, key linking orbitals between metal and macrocycle. Through a correlated breathing mechanism, the 3d electrons can make transitions towards the pi orbitals of the macrocycle. This guarantees a strong coupling between the on-site radial correlation on the metal and electron delocalization. Opposite-spin 3d electrons of the triplet can effectively reduce electron repulsion in this manner. Constraining the out-of-plane orbitals from breathing hinders delocalization and reverses the spin ordering. Our results find a qualitative analogue in Kekul\'e resonance structures involving also the metal centre.